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Sample records for chiral olefin metathesis

  1. Olefin metathesis in air

    PubMed Central

    Piola, Lorenzo; Nahra, Fady

    2015-01-01

    Summary Since the discovery and now widespread use of olefin metathesis, the evolution of metathesis catalysts towards air stability has become an area of significant interest. In this fascinating area of study, beginning with early systems making use of high oxidation state early transition metal centers that required strict exclusion of water and air, advances have been made to render catalysts more stable and yet more functional group tolerant. This review summarizes the major developments concerning catalytic systems directed towards water and air tolerance. PMID:26664625

  2. Microwave-Assisted Olefin Metathesis

    NASA Astrophysics Data System (ADS)

    Nicks, François; Borguet, Yannick; Sauvage, Xavier; Bicchielli, Dario; Delfosse, Sébastien; Delaude, Lionel; Demonceau, Albert

    Since the first reports on the use of microwave irradiation to accelerate organic chemical transformations, a plethora of papers have been published in this field. In most examples, microwave heating has been shown to dramatically reduce reaction times, increase product yields, and enhance product purity by reducing unwanted side reactions compared to conventional heating methods. The present contribution aims at illustrating the advantages of this technology in olefin metathesis and, when data are available, at comparing microwave-heated and conventionally heated experiments

  3. Olefin metathesis in nano-sized systems

    PubMed Central

    Diallo, Abdou K; Gatard, Sylvain; Liang, Liyuan; Ornelas, Cátia; Martinez, Victor; Méry, Denise; Ruiz, Jaime

    2011-01-01

    Summary The interplay between olefin metathesis and dendrimers and other nano systems is addressed in this mini review mostly based on the authors’ own contributions over the last decade. Two subjects are presented and discussed: (i) The catalysis of olefin metathesis by dendritic nano-catalysts via either covalent attachment (ROMP) or, more usefully, dendrimer encapsulation – ring closing metathesis (RCM), cross metathesis (CM), enyne metathesis reactions (EYM) – for reactions in water without a co-solvent and (ii) construction and functionalization of dendrimers by CM reactions. PMID:21286399

  4. Methods for suppressing isomerization of olefin metathesis products

    DOEpatents

    Firth, Bruce E.; Kirk, Sharon E.; Gavaskar, Vasudeo S.

    2015-09-22

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. The isomerization suppression agent is phosphorous acid, a phosphorous acid ester, phosphinic acid, a phosphinic acid ester or combinations thereof. Methods of refining natural oils are described.

  5. Methods for suppressing isomerization of olefin metathesis products

    DOEpatents

    Firth, Bruce E.; Kirk, Sharon E.

    2015-10-27

    A method for suppressing isomerization of an olefin metathesis product produced in a metathesis reaction includes adding an isomerization suppression agent that includes nitric acid to a mixture that includes the olefin metathesis product and residual metathesis catalyst from the metathesis reaction under conditions that are sufficient to passivate at least a portion of the residual metathesis catalyst. Methods of refining a natural oil are described.

  6. Enantioselective Olefin Metathesis with Cyclometalated Ruthenium Complexes

    PubMed Central

    2015-01-01

    The success of enantioselective olefin metathesis relies on the design of enantioenriched alkylidene complexes capable of transferring stereochemical information from the catalyst structure to the reactants. Cyclometalation of the NHC ligand has proven to be a successful strategy to incorporate stereogenic atoms into the catalyst structure. Enantioenriched complexes incorporating this design element catalyze highly Z- and enantioselective asymmetric ring opening/cross metathesis (AROCM) of norbornenes and cyclobutenes, and the difference in ring strain between these two substrates leads to different propagating species in the catalytic cycle. Asymmetric ring closing metathesis (ARCM) of a challenging class of prochiral trienes has also been achieved. The extent of reversibility and effect of reaction setup was also explored. Finally, promising levels of enantioselectivity in an unprecedented Z-selective asymmetric cross metathesis (ACM) of a prochiral 1,4-diene was demonstrated. PMID:25137310

  7. Thermally Stable, Latent Olefin Metathesis Catalysts

    PubMed Central

    Thomas, Renee M.; Fedorov, Alexey; Keitz, Benjamin K.

    2011-01-01

    Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to induce latent behavior toward cross-metathesis reactions, and exchange of the chloride ligands for iodide ligands was necessary to attain latent behavior during ring-opening metathesis polymerization (ROMP). Iodide-based catalysts showed no reactivity toward ROMP of norbornene-derived monomers at 25 °C, and upon heating to 85 °C gave complete conversion of monomer to polymer in less than 2 hours. All of the complexes were very stable to air, moisture, and elevated temperatures up to at least 90 °C, and exhibited a long catalyst lifetime in solution at elevated temperatures. PMID:22282652

  8. Stereoretentive Olefin Metathesis: An Avenue to Kinetic Selectivity.

    PubMed

    Montgomery, T Patrick; Ahmed, Tonia S; Grubbs, Robert H

    2017-09-04

    Olefin metathesis is an incredibly valuable transformation that has gained widespread use in both academic and industrial settings. Lately, stereoretentive olefin metathesis has garnered much attention as a method for the selective generation of both E- and Z-olefins. Early studies employing ill-defined catalysts showed evidence for retention of the stereochemistry of the starting olefins at low conversion. However, thermodynamic ratios E/Z were reached as the reaction proceeded to equilibrium. Recent studies in olefin metathesis have focused on the synthesis of catalysts that can overcome the inherent thermodynamic preference of an olefin, providing synthetically useful quantities of a kinetically favored olefin isomer. These reports have led to the development of stereoretentive catalysts that not only generate Z-olefins selectively, but also kinetically produce E-olefins, a previously unmet challenge in olefin metathesis. Advancements in stereoretentive olefin metathesis using tungsten, ruthenium, and molybdenum catalysts are presented. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Iron(III)-catalysed carbonyl-olefin metathesis

    NASA Astrophysics Data System (ADS)

    Ludwig, Jacob R.; Zimmerman, Paul M.; Gianino, Joseph B.; Schindler, Corinna S.

    2016-05-01

    The olefin metathesis reaction of two unsaturated substrates is one of the most powerful carbon-carbon-bond-forming reactions in organic chemistry. Specifically, the catalytic olefin metathesis reaction has led to profound developments in the synthesis of molecules relevant to the petroleum, materials, agricultural and pharmaceutical industries. These reactions are characterized by their use of discrete metal alkylidene catalysts that operate via a well-established mechanism. While the corresponding carbonyl-olefin metathesis reaction can also be used to construct carbon-carbon bonds, currently available methods are scarce and severely hampered by either harsh reaction conditions or the required use of stoichiometric transition metals as reagents. To date, no general protocol for catalytic carbonyl-olefin metathesis has been reported. Here we demonstrate a catalytic carbonyl-olefin ring-closing metathesis reaction that uses iron, an Earth-abundant and environmentally benign transition metal, as a catalyst. This transformation accommodates a variety of substrates and is distinguished by its operational simplicity, mild reaction conditions, high functional-group tolerance, and amenability to gram-scale synthesis. We anticipate that these characteristics, coupled with the efficiency of this reaction, will allow for further advances in areas that have historically been enhanced by olefin metathesis.

  10. Metathesis process for preparing an alpha, omega-functionalized olefin

    DOEpatents

    Burdett, Kenneth A.; Mokhtarzadeh, Morteza; Timmers, Francis J.

    2010-10-12

    A cross-metathesis process for preparing an .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, and an .alpha.-olefin having three or more carbon atoms, such as 1-decene. The process involves contacting in a first reaction zone an .alpha.-functionalized internal olefin, such as methyl oleate, and an .alpha.-olefinic monomer having three or more carbon atoms, such as 1-decene, with a first metathesis catalyst to prepare an effluent stream containing the .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, an unfunctionalized internal olefin, such as 9-octadecene, unconverted reactant olefins, and optionally, an .alpha.,.omega.-difunctionalized internal olefinic dimer, such as dimethyl 9-octadecen-1,18-dioate; separating said effluent streams; then contacting in a second reaction zone the unfunctionalized internal olefin with ethylene in the presence of a second metathesis catalyst to obtain a second product effluent containing the .alpha.-olefinic monomer having three or more carbon atoms; and cycling a portion of the .alpha.-olefinic monomer stream(s) to the first zone.

  11. Synthesis of interlocked molecules by olefin metathesis

    NASA Astrophysics Data System (ADS)

    Clark, Paul Gregory

    A large body of work in the Grubbs group has focused on the development of functional-group tolerant ruthenium alkylidene catalysts that perform a number of olefin metathesis reactions. These catalysts have seen application in a wide range of fields, including classic total synthesis as well as polymer and materials chemistry. One particular family of compounds, interlocked molecules, has benefitted greatly from these advances in catalyst stability and activity. This thesis describes several elusive and challenging interlocked architectures whose syntheses have been realized through the utilization of different types of ruthenium-catalyzed olefin metathesis reactions. Ring-closing olefin metathesis has enabled the synthesis of a [c2]daisy-chain dimer with the ammonium binding site near the cap of the dimer. A deprotonated DCD possessing such a structural attribute will more forcefully seek to restore coordinating interactions upon reprotonation, enhancing its utility as a synthetic molecular actuator. Dimer functionalization facilitated incorporation into linear polymers, with a 48% size increase of an unbound, extended analogue of the polymer demonstrating slippage of the dimer units. Ongoing work is directed at further materials studies, in particular, exploring the synthesis of macroscopic networks containing the DCD units and analyzing the correlation between molecular-scale extension-contraction manipulations and resulting macro-scale changes. A "clipping" approach to a polycatenated cyclic polymer, a structure that resembles a molecular "charm bracelet", has been described. The use of ring-opening metathesis polymerization of a carbamate monomer in the presence of a chain transfer agent allowed for the synthesis of a linear polymer that was subsequently functionalized and cyclized to the corresponding cyclic analogue. This cyclic polymer was characterized through a variety of techniques, and subjected to further functionalization reactions, affording a cyclic

  12. Mesoporous Molecular Sieves Based Catalysts for Olefin Metathesis and Metathesis Polymerization

    NASA Astrophysics Data System (ADS)

    Balcar, Hynek; Čejka, Jiří

    Heterogeneous catalysts for olefin metathesis using different types of (i) siliceous mesoporous molecular sieves, and (ii) organized mesoporous alumina as supports are reported. The catalysts were prepared either by spreading of transition metal oxidic phase on the support surface or by immobilizing transition metal compounds (mostly organometallic) on the support. The activity of these catalysts in various types of metathesis reactions (i.e. alkene and diene metathesis, metathesis of unsaturated esters and ethers, RCM, ROMP and metathesis polymerization of alkynes) was described. The main advantages of these catalysts consist generally in their high activity and selectivity, easy separation of catalysts from reaction products and the preparation of products free of catalyst residue. The examples of pore size influence on the selectivity in metathesis reactions are also given.

  13. Homobimetallic Ruthenium-N-Heterocyclic Carbene Complexes For Olefin Metathesis

    NASA Astrophysics Data System (ADS)

    Sauvage, Xavier; Demonceau, Albert; Delaude, Lionel

    In this chapter, the synthesis and catalytic activity towards olefin metathesis of homobimetallic ruthenium (Ru)-alkylidene, -cyclodiene or -arene complexes bearing phosphine or N-heterocyclic carbene (NHC) ligands are reviewed. Emphasis is placed on the last category of bimetallic compounds. Three representatives of this new type of molecular scaffold were investigated. Thus, [(p-cymene)Ru(m-Cl)3RuCl (h2-C2H4)(L)] complexes with L = PCy3 (15a), IMes (16a), or IMesCl2 (16b) were prepared. They served as catalyst precursors for cross-metathesis (CM) of various styrene derivatives. These experiments revealed the outstanding aptitude of complex 16a (and to a lesser extent of 16b) to catalyze olefin metathesis reactions. Contrary to monometallic Ru-arene complexes of the [RuCl2(p-cymene)(L)] type, the new homobimetallic species did not require the addition of a diazo compound nor visible light illumination to initiate the ring-opening metathesis of norbornene or cyclooctene. When diethyl 2,2-diallylmalonate and N,N-diallyltosylamide were exposed to 16a,b, a mixture of cycloisomerization and ring-closing metathesis (RCM) products was obtained in a nonselective way. Addition of phenylacetylene enhanced the metathetical activity while completely repressing the cycloisomerization process.

  14. Refining of plant oils to chemicals by olefin metathesis.

    PubMed

    Chikkali, Samir; Mecking, Stefan

    2012-06-11

    Plant oils are attractive substrates for the chemical industry. Their scope for the production of chemicals can be expanded by sophisticated catalytic conversions. Olefin metathesis is an example, which also illustrates generic issues of "biorefining" to chemicals. Utilization on a large scale requires high catalyst activities, which influences the choice of the metathesis reaction. The mixture of different fatty acids composing a technical-grade plant oil substrate gives rise to a range of products. This decisively determines possible process schemes, and potentially provides novel chemicals and intermediates not employed to date.

  15. Enhanced Olefin Cross Metathesis Reactions: The Copper Iodide Effect

    PubMed Central

    Voigtritter, Karl; Ghorai, Subir

    2011-01-01

    Copper iodide has been shown to be an effective co-catalyst for the olefin cross metathesis reaction. In particular, it has both a catalyst stabilizing effect due to iodide ion, as well as copper(I)-based phosphine-scavenging properties that apply to use of the Grubbs-2 catalyst. A variety of Michael acceptors and olefinic partners can be cross-coupled under mild conditions in refluxing diethyl ether that avoid chlorinated solvents. This effect has also been applied to chemistry in water at room temperature using the new surfactant TPGS-750-M. PMID:21528868

  16. Highly Z-Selective Metathesis Homocoupling of Terminal Olefins

    PubMed Central

    Jiang, Annie J.; Zhao, Yu; Schrock, Richard R.; Hoveyda, Amir H.

    2009-01-01

    Mo and W MonoAryloxide-Pyrrolide (MAP) olefin metathesis catalysts can couple terminal olefins to give as high as >98% Z-products in moderate to high yields with as little as 0.2% catalyst. Results are reported for 1-hexene, 1-octene, allylbenzene, allyltrimethylsilane, methyl-10-undecenoate, methyl-9-decenoate, allylB(pinacolate), allylOBenzyl, allylNHTosyl, and allylNHPh. It is proposed that high Z-selectivity is achieved because a large aryloxide only allows metallacyclobutanes to form that contain adjacent cis substituents and because isomerization of Z-product to E-product can be slow in that same steric environment. PMID:19919135

  17. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2013-07-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  18. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann [Agoura Hills, CA

    2011-11-29

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  19. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2015-09-22

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  20. Synthesis of terminal alkenes from internal alkenes and ethylene via olefin metathesis

    DOEpatents

    Schrodi, Yann

    2016-02-09

    This invention relates generally to olefin metathesis, and more particularly relates to the synthesis of terminal alkenes from internal alkenes using a cross-metathesis reaction catalyzed by a selected olefin metathesis catalyst. In one embodiment of the invention, for example, a method is provided for synthesizing a terminal olefin, the method comprising contacting an olefinic substrate comprised of at least one internal olefin with ethylene, in the presence of a metathesis catalyst, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate, and wherein the metathesis catalyst has the structure of formula (II) ##STR00001## wherein the various substituents are as defined herein. The invention has utility, for example, in the fields of catalysis, organic synthesis, and industrial chemistry.

  1. Iron(III)-Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    PubMed

    Saá, Carlos

    2016-09-05

    Recent developments in catalytic carbonyl-olefin metathesis are summarized in this Highlight. Schindler and co-workers have reported that the environmentally benign FeCl3 catalyst promotes ring-closing carbonyl-olefin metathesis (RCCOM) in high yield under very mild conditions. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. FeCl3 -Catalyzed Ring-Closing Carbonyl-Olefin Metathesis.

    PubMed

    Ma, Lina; Li, Wenjuan; Xi, Hui; Bai, Xiaohui; Ma, Enlu; Yan, Xiaoyu; Li, Zhiping

    2016-08-22

    Exploiting catalytic carbonyl-olefin metathesis is an ongoing challenge in organic synthesis. Reported herein is an FeCl3 -catalyzed ring-closing carbonyl-olefin metathesis. The protocol allows access to a range of carbo-/heterocyclic alkenes with good efficiency and excellent trans diastereoselectivity. The methodology presents one of the rare examples of catalytic ring-closing carbonyl-olefin metathesis. This process is proposed to take place by FeCl3 -catalyzed oxetane formation followed by retro-ring-opening to deliver metathesis products. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Ruthenium olefin metathesis catalysts featuring unsymmetrical N-heterocyclic carbenes.

    PubMed

    Paradiso, Veronica; Bertolasi, Valerio; Costabile, Chiara; Grisi, Fabia

    2016-01-14

    New ruthenium Grubbs' and Hoveyda-Grubbs' second generation catalysts bearing N-alkyl/N-isopropylphenyl N-heterocyclic carbene (NHC) ligands with syn or anti backbone configuration were obtained and compared in model olefin metathesis reactions. Different catalytic efficiencies were observed depending on the size of the N-alkyl group (methyl or cyclohexyl) and on the backbone configuration. The presence of an N-cyclohexyl substituent determined the most significant reactivity differences between catalysts with syn or anti phenyl groups on the backbone. In particular, anti catalysts proved highly efficient, especially in the ring-closing metathesis (RCM) of encumbered diolefins, while syn catalysts showed low efficiency in the RCM of less hindered diolefins. This peculiar behavior, rationalized through DFT studies, was found to be related to the high propensity of these catalysts to give nonproductive metathesis events. Enantiopure anti catalysts were also tested in asymmetric metathesis reactions, where moderate enantioselectivities were observed. The steric and electronic properties of unsymmetrical NHCs with the N-cyclohexyl group were then evaluated using the corresponding rhodium complexes. While steric factors proved unimportant for both syn and anti NHCs, a major electron-donating character was found for the unsymmetrical NHC with anti phenyl substituents on the backbone.

  4. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions

    NASA Astrophysics Data System (ADS)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  5. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions.

    PubMed

    Koh, Ming Joo; Nguyen, Thach T; Lam, Jonathan K; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R; Hoveyda, Amir H

    2017-02-02

    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  6. A Ruthenium Catalyst for Olefin Metathesis Featuring an Anti-Bredt N-Heterocyclic Carbene Ligand

    PubMed Central

    Martin, David; Marx, Vanessa M.

    2016-01-01

    A ruthenium complex bearing an “anti-Bredt” N-heterocyclic carbene was synthesized, characterized and evaluated as a catalyst for olefin metathesis. Good conversions were observed at room temperature for the formation of di- and tri-substituted olefins by ring-closing metathesis. It also allowed for the ring-opening metathesis polymerization of cyclooctadiene, as well as for the cross-metathesis of cis-1,4-diacetoxy-2-butene with allyl-benzene, with enhanced Z/E kinetic selectivity over classical NHC-based catalysts. PMID:27594819

  7. Olefin metathesis for effective polymer healing via dynamic exchange of strong carbon-carbon bonds

    DOEpatents

    Guan, Zhibin; Lu, Yixuan

    2015-09-15

    A method of preparing a malleable and/or self-healing polymeric or composite material is provided. The method includes providing a polymeric or composite material comprising at least one alkene-containing polymer, combining the polymer with at least one homogeneous or heterogeneous transition metal olefin metathesis catalyst to form a polymeric or composite material, and performing an olefin metathesis reaction on the polymer so as to form reversible carbon-carbon double bonds in the polymer. Also provided is a method of healing a fractured surface of a polymeric material. The method includes bringing a fractured surface of a first polymeric material into contact with a second polymeric material, and performing an olefin metathesis reaction in the presence of a transition metal olefin metathesis catalyst such that the first polymeric material forms reversible carbon-carbon double bonds with the second polymeric material. Compositions comprising malleable and/or self-healing polymeric or composite material are also provided.

  8. Aromatizing olefin metathesis by ligand isolation inside a metal-organic framework.

    PubMed

    Vermeulen, Nicolaas A; Karagiaridi, Olga; Sarjeant, Amy A; Stern, Charlotte L; Hupp, Joseph T; Farha, Omar K; Stoddart, J Fraser

    2013-10-09

    The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

  9. Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

    PubMed Central

    Lafaye, Kevin; Bosset, Cyril; Nicolas, Lionel

    2015-01-01

    Summary Alkenes containing N-heteroaromatics are known to be poor partners in cross-metathesis reactions, probably due to catalyst deactivation caused by the presence of a nitrogen atom. However, some examples of ring-closing and cross-metathesis involving alkenes that incorporate N-heteroaromatics can be found in the literature. In addition, recent mechanistic studies have focused on the rationalization of nitrogen-induced catalysts deactivation. The purpose of this mini-review is to give a brief overview of successful metathesis reactions involving olefins containing N-heteroaromatics in order to delineate some guidelines for the use of these challenging substrates in metathesis reactions. PMID:26664645

  10. Synthesis of the EF-ring of ciguatoxin 3C based on the [2,3]-Wittig rearrangement and ring-closing olefin metathesis.

    PubMed

    Goto, Akiyoshi; Fujiwara, Kenshu; Kawai, Ayako; Kawai, Hidetoshi; Suzuki, Takanori

    2007-12-20

    The EF-ring segment of ciguatoxin 3C, a causative toxin of ciguatera fish poisoning, was synthesized in three major steps: 1,4-addition for the C20O-C27 bond connection, chirality transferring anti selective [2,3]-Wittig rearrangement for the construction of the anti-2-hydroxyalkyl ether part, and ring-closing olefin metathesis for the F-ring formation.

  11. Enantioselective synthesis of 5-epi-citreoviral using ruthenium-catalyzed asymmetric ring-closing metathesis.

    PubMed

    Funk, Timothy W

    2009-11-05

    Chiral ruthenium olefin metathesis catalysts can perform asymmetric ring-closing reactions in > or = 90% ee with low catalyst loadings. To illustrate the practicality of these reactions and the products they form, an enantioselective total synthesis of 5-epi-citreoviral was completed by using an asymmetric ring-closing olefin metathesis reaction as a key step early in the synthesis. All of the stereocenters in the final compound were set by using the chiral center generated by asymmetric olefin metathesis.

  12. Sunflower-based Feedstocks in Nonfood Applications: Perspectives from Olefin Metathesis

    PubMed Central

    Marvey, Bassie B.

    2008-01-01

    Sunflower (Helianthus annuus L.) oil remains under-utilised albeit one of the major seed oils produced world-wide. Moreover, the high oleic sunflower varieties make the oil attractive for applications requiring high temperature processes and those targeting the C=C double bond functionality. Herein an overview of the recent developments in olefin metathesis of sunflower-based feedstocks is presented. The improved performance of olefin metathesis catalysts leading to high turnover numbers, high selectivity and catalyst recyclability, opens new opportunities for tailoring sunflower-based feedstocks into products required for possible new niche market applications. Promising results in biofuel, biopolymers, fragrances and fine chemicals applications have been reported. PMID:19325810

  13. Olefin Metathesis in Homogeneous Aqueous Media Catalyzed by Conventional Ruthenium Catalysts

    PubMed Central

    Binder, Joseph B.; Blank, Jacqueline J.; Raines, Ronald T.

    2008-01-01

    Olefin metathesis in aqueous solvents is sought for applications in green chemistry and with the hydrophilic substrates of chemical biology, such as proteins and polysaccharides. Most demonstrations of metathesis in water, however, utilize exotic complexes. We have examined the performance of conventional catalysts in homogeneous water–organic mixtures, finding that the second-generation Hoveyda–Grubbs catalyst has extraordinary efficiency in aqueous dimethoxyethane and aqueous acetone. High (71–95%) conversions are achieved for ring-closing and cross metathesis of a variety of substrates in these solvent systems. PMID:17949009

  14. The Olefin Metathesis Reactions Combined with Organo-Iron Arene Activation Towards Dendrimers, and Polymers

    NASA Astrophysics Data System (ADS)

    Astruc, Didier; Martinez, Victor

    The subjects treated in the two lectures of the North Atlantic Treaty Organization (NATO) summer course are (1) the combination of arene activation and perfunctionalization using organo-iron chemistry with olefin metathesis incuding metathesis of dendritic polyolefin molecules; (2) the synthesis of metallodendritic benzylidene complexes that catalyse ring-opening metathesis polymerization (ROMP) under ambient conditions and the formation of dendritic stars; (3) the use of stoichiometric and catalytic electron-transfer processes with standard reservoirs of electrons (reductants) or electron holes (oxidants) iron complexes to achieve noteworthy metathesis reactions or synthesize compounds that are useful in metathesis. Only the two first topics are treated in this chapter, and interested readers can find references concerning the third aspect called in the introduction and subsequently cited in the reference list.

  15. Amphiphilic Cellulose Ethers Designed for Amorphous Solid Dispersion via Olefin Cross-Metathesis.

    PubMed

    Dong, Yifan; Mosquera-Giraldo, Laura I; Taylor, Lynne S; Edgar, Kevin J

    2016-02-08

    The design of cellulose ether-based amphiphiles has been difficult and limited because of the harsh conditions typically required for appending ether moieties to cellulose. Olefin cross-metathesis recently has been shown to be a valuable approach for appending a variety of functional groups to cellulose ethers and esters, provided that an olefin handle for metathesis can be attached. This synthetic pathway gives access to these functional derivatives under very mild conditions and at high efficiency. Modification of ethyl cellulose by metathesis to prepare useful derivatives, for example, for solubility and bioavailability enhancement of drugs by amorphous solid dispersion (ASD), has been limited by the low DS(OH) of commercial ethyl cellulose derivatives. This is problematic because ethyl cellulose is otherwise a very attractive substrate for synthesis of amphiphilic derivatives by olefin metathesis. Herein we explore two methods for opening up this design space for ether-based amphiphiles, for example, permitting synthesis of more hydrophilic derivatives. One approach is to start with the more hydrophilic commercial methyl cellulose, which contains much higher DS(OH) and therefore is better suited for introduction of high DS of olefin metathesis "handles". In another approach, we explored a homogeneous one-pot synthesis methodology from cellulose, where controlled DS of ethyl groups was introduced at the same time as the ω-unsaturated alkyl groups, thereby permitting complete control of DS(OH), DS(Et), and ultimately DS of the functional group added by metathesis. We describe the functionalized derivatives available by these successful approaches. In addition, we explore new methods for reduction of the unsaturation in initial metathesis products to provide robust methods for enhancing product stability against further radical-catalyzed reactions. We demonstrate initial evidence that the products show strong promise as amphiphilic matrix polymers for amorphous

  16. Z-Selective Olefin Metathesis on Peptides: Investigation of Side-Chain Influence, Preorganization, and Guidelines in Substrate Selection

    PubMed Central

    2015-01-01

    Olefin metathesis has emerged as a promising strategy for modulating the stability and activity of biologically relevant compounds; however, the ability to control olefin geometry in the product remains a challenge. Recent advances in the design of cyclometalated ruthenium catalysts has led to new strategies for achieving such control with high fidelity and Z selectivity, but the scope and limitations of these catalysts on substrates bearing multiple functionalities, including peptides, remained unexplored. Herein, we report an assessment of various factors that contribute to both productive and nonproductive Z-selective metathesis on peptides. The influence of sterics, side-chain identity, and preorganization through peptide secondary structure are explored by homodimerization, cross metathesis, and ring-closing metathesis. Our results indicate that the amino acid side chain and identity of the olefin profoundly influence the activity of cyclometalated ruthenium catalysts in Z-selective metathesis. The criteria set forth for achieving high conversion and Z selectivity are highlighted by cross metathesis and ring-closing metathesis on diverse peptide substrates. The principles outlined in this report are important not only for expanding the scope of Z-selective olefin metathesis to peptides but also for applying stereoselective olefin metathesis in general synthetic endeavors. PMID:25102124

  17. Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst

    EPA Science Inventory

    The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or co-solvents, in a short period of time. We found that inhomogen...

  18. Olefin Ring Closing Metathesis and Hydrosilylation Reaction in Aqueous Medium by Grubbs Second Generation Ruthenium Catalyst

    EPA Science Inventory

    The Grubbs second generation ruthenium catalyst was shown to catalyze various olefin ring closing metathesis and hydrosilylation reactions in aqueous medium. Reactions proceeded in pure water without any additives or co-solvents, in a short period of time. We found that inhomogen...

  19. Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory

    ERIC Educational Resources Information Center

    Greco, George E.

    2007-01-01

    An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

  20. Nobel Chemistry in the Laboratory: Synthesis of a Ruthenium Catalyst for Ring-Closing Olefin Metathesis--An Experiment for the Advanced Inorganic or Organic Laboratory

    ERIC Educational Resources Information Center

    Greco, George E.

    2007-01-01

    An experiment for the upper-level undergraduate laboratory is described in which students synthesize a ruthenium olefin metathesis catalyst, then use the catalyst to carry out the ring-closing metathesis of diethyl diallylmalonate. The olefin metathesis reaction was the subject of the 2005 Nobel Prize in chemistry. The catalyst chosen for this…

  1. "Click" and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles.

    PubMed

    Lipshutz, Bruce H; Bošković, Zarko; Crowe, Christopher S; Davis, Victoria K; Whittemore, Hannah C; Vosburg, David A; Wenzel, Anna G

    2013-11-12

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide-alkyne "click" reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide-alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis).

  2. “Click” and Olefin Metathesis Chemistry in Water at Room Temperature Enabled by Biodegradable Micelles

    PubMed Central

    Lipshutz, Bruce H.; Bošković, Zarko; Crowe, Christopher S.; Davis, Victoria K.; Whittemore, Hannah C.; Vosburg, David A.; Wenzel, Anna G.

    2013-01-01

    The two laboratory reactions focus on teaching several concepts associated with green chemistry. Each uses a commercial, nontoxic, and biodegradable surfactant, TPGS-750-M, to promote organic reactions within the lipophilic cores of nanoscale micelles in water. These experiments are based on work by K. Barry Sharpless (an azide–alkyne “click” reaction) and Robert Grubbs (an olefin cross-metathesis reaction); both are suitable for an undergraduate organic laboratory. The copper-catalyzed azide–alkyne [3+2] cycloaddition of benzyl azide and 4-tolylacetylene is very rapid: the triazole product is readily isolated by filtration and is characterized by thin-layer chromatography and melting point analysis. The ruthenium-catalyzed olefin cross-metathesis reaction of benzyl acrylate with 1-hexene is readily monitored by thin-layer chromatography and gas chromatography. The metathesis experiment comparatively evaluates the efficacy of a TPGS-750-M/water medium relative to a traditional reaction performed in dichloromethane (a common solvent used for olefin metathesis). PMID:24324282

  3. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach.

    PubMed

    Mangold, Shane L; Grubbs, Robert H

    2015-08-01

    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E- and Z-olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E- or Z-olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM.

  4. Stereoselective synthesis of macrocyclic peptides via a dual olefin metathesis and ethenolysis approach

    PubMed Central

    Mangold, Shane L.

    2015-01-01

    Macrocyclic compounds occupy an important chemical space between small molecules and biologics and are prevalent in many natural products and pharmaceuticals. The growing interest in macrocycles has been fueled, in part, by the design of novel synthetic methods to these compounds. One appealing strategy is ring-closing metathesis (RCM) that seeks to construct macrocycles from acyclic diene precursors using defined transition-metal alkylidene catalysts. Despite its broad utility, RCM generally gives rise to a mixture of E- and Z-olefin isomers that can hinder efforts for the large-scale production and isolation of such complex molecules. To address this issue, we aimed to develop methods that can selectively enrich macrocycles in E- or Z-olefin isomers using an RCM/ethenolysis strategy. The utility of this methodology was demonstrated in the stereoselective formation of macrocyclic peptides, a class of compounds that have gained prominence as therapeutics in drug discovery. Herein, we report an assessment of various factors that promote catalyst-directed RCM and ethenolysis on a variety of peptide substrates by varying the olefin type, peptide sequence, and placement of the olefin in macrocycle formation. These methods allow for control over olefin geometry in peptides, facilitating their isolation and characterization. The studies outlined in this report seek to expand the scope of stereoselective olefin metathesis in general RCM. PMID:26509000

  5. Nobel Prize in Chemistry. Development of the Olefin Metathesis Method in Organic Synthesis

    NASA Astrophysics Data System (ADS)

    Casey, Charles P.

    2006-02-01

    The 2005 Nobel Prize in Chemistry was awarded to Yves Chauvin of the Institut Français du Pétrole, Robert H. Grubbs of CalTech, and Richard R. Schrock of MIT "for development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction now used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other products. This article tells the story of how olefin metathesis became a truly useful synthetic transformation and a triumph for mechanistic chemistry, and illustrates the importance of fundamental research. See JCE Featured Molecules .

  6. Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis

    PubMed Central

    Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A.; Dąbrowski, Paweł

    2016-01-01

    Abstract The state‐of‐the‐art in olefin metathesis is application of N‐heterocyclic carbene (NHC)‐containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)‐containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported. PMID:27943616

  7. Bis(Cyclic Alkyl Amino Carbene) Ruthenium Complexes: A Versatile, Highly Efficient Tool for Olefin Metathesis.

    PubMed

    Gawin, Rafał; Kozakiewicz, Anna; Guńka, Piotr A; Dąbrowski, Paweł; Skowerski, Krzysztof

    2017-01-19

    The state-of-the-art in olefin metathesis is application of N-heterocyclic carbene (NHC)-containing ruthenium alkylidenes for the formation of internal C=C bonds and of cyclic alkyl amino carbene (CAAC)-containing ruthenium benzylidenes in the production of terminal olefins. A straightforward synthesis of bis(CAAC)Ru indenylidene complexes, which are highly effective in the formation of both terminal and internal C=C bonds at loadings as low as 1 ppm, is now reported.

  8. Linker-free, silica-bound olefin-metathesis catalysts: applications in heterogeneous catalysis.

    PubMed

    Cabrera, José; Padilla, Robin; Bru, Miriam; Lindner, Ronald; Kageyama, Takeharu; Wilckens, Kristina; Balof, Shawna L; Schanz, Hans-Jörg; Dehn, Richard; Teles, J Henrique; Deuerlein, Stephan; Müller, Kevin; Rominger, Frank; Limbach, Michael

    2012-11-12

    A set of heterogenized olefin-metathesis catalysts, which consisted of Ru complexes with the H(2)ITap ligand (1,3-bis(2',6'-dimethyl-4'dimethyl aminophenyl)-4,5-dihydroimidazol-2-ylidene) that had been adsorbed onto a silica support, has been prepared. These complexes showed strong binding to the solid support without the need for tethering groups on the complex or functionalized silica. The catalysts were tested in the ring-opening-ring-closing-metathesis (RO-RCM) of cyclooctene (COE) and the self-metathesis of methyl oleate under continuous-flow conditions. The best complexes showed a TON>4000, which surpasses the previously reported materials that were either based on the Grubbs-Hoveyda II complex on silica or on the classical heterogeneous Re(2)O(7)/B(2)O(3) catalyst.

  9. Biopolymer-supported ionic-liquid-phase ruthenium catalysts for olefin metathesis.

    PubMed

    Clousier, Nathalie; Filippi, Alexandra; Borré, Etienne; Guibal, Eric; Crévisy, Christophe; Caijo, Fréderic; Mauduit, Marc; Dez, Isabelle; Gaumont, Annie-Claude

    2014-04-01

    Original ruthenium supported ionic liquid phase (SILP) catalysts based on alginates as supports were developed for olefin metathesis reactions. The marine biopolymer, which fulfills most of the requisite properties for a support such as widespread abundance, insolubility in the majority of organic solvents, a high affinity for ionic liquids, high chemical stability, biodegradability, low cost, and easy processing, was impregnated by [bmim][PF6 ] containing an ionically tagged ruthenium catalyst. These biosourced catalysts show promising performances in ring-closing metathesis (RCM) and cross-metathesis (CM) reactions, with a high level of recyclability and reusability combined with a good reactivity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

    PubMed Central

    Žilková, Naděžda; Kubů, Martin; Mazur, Michal; Bastl, Zdeněk; Čejka, Jiří

    2015-01-01

    Summary Hoveyda–Grubbs type catalysts with cationic tags on NHC ligands were linker-free immobilized on the surface of lamellar zeolitic supports (MCM-22, MCM-56, MCM-36) and on mesoporous molecular sieves SBA-15. The activity of prepared hybrid catalysts was tested in olefin metathesis reactions: the activity in ring-closing metathesis of citronellene and N,N-diallyltrifluoroacetamide decreased in the order of support MCM-22 ≈ MCM-56 > SBA-15 > MCM-36; the hybrid catalyst based on SBA-15 was found the most active in self-metathesis of methyl oleate. All catalysts were reusable and exhibited low Ru leaching (<1% of Ru content). XPS analysis revealed that during immobilization ion exchange between Hoveyda–Grubbs type catalyst and zeolitic support occurred in the case of Cl− counter anion; in contrast, PF6 − counter anion underwent partial decomposition. PMID:26664629

  11. Self-selection in olefin cross-metathesis: the effect of remote functionality.

    PubMed

    McNaughton, Brian R; Bucholtz, Kevin M; Camaaño-Moure, Ana; Miller, Benjamin L

    2005-02-17

    Olefin cross-metathesis (CM) is potentially an attractive method for generating dynamic combinatorial libraries (DCLs). In order for the CM reaction to be useful for DCL production, the course of the reaction and product distribution must be relatively insensitive to functionality remote from the reacting centers. We report on the CM of a series of allyl- and homoallylamides that are strongly dependent on remote functionality. This includes an unusual example of a cis-selective CM. [Reaction: see text

  12. Ruthenium indenylidene “1st generation” olefin metathesis catalysts containing triisopropyl phosphite

    PubMed Central

    Guidone, Stefano; Nahra, Fady; Slawin, Alexandra M Z

    2015-01-01

    Summary The reaction of triisopropyl phosphite with phosphine-based indenylidene pre-catalysts affords “1st generation” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L-type ligands. PMID:26425210

  13. Solvent-free cyclization of linear dienes using olefin metathesis and the Thorpe-Ingold effect

    SciTech Connect

    Forbees, M.D.E.; Myers, T.L.; Maynard, H.D.; Schulz, G.R. ); Patton, J.T.; Smith, D.W. Jr.; Wagener, K.B. )

    1992-12-30

    The olefin metathesis reaction is of great synthetic utility in polymer chemistry. The recent development of ring-opening (ROMP) and acyclic diene (ADMET) metathesis polymerization reactions has opened new avenues for the synthesis of novel polymeric materials. Recently the authors used ADMET to synthesize several photochemically active poly(keto olefins) using the catalyst Mo(CHCMe[sub 2]Ph)(NAr)(OCMe(CF[sub 3])[sub 2])[sub 2] (Ar = 2,6-diisopropylphenyl) (1) developed by Schrock and co-workers in 1990. In the course of that work, they discovered that neat samples of highly substituted dienes will cyclize quantitatively via metathesis to give difunctional five- and seven-membered rings instead of the expected linear polymer. Examples of substituted diene cyclizations by metathesis even in the presence of a solvent are rare. Their systematic exploitation in organic synthesis has therefore been limited to two recent studies by Fu and Grubbs, who cyclized several substituted diene ethers, amines, and amides to unsaturated oxygen and nitrogen heterocycles. Cyclization of unsubstituted dienes in various solvents has been reported, but complete conversion occurred in only a few cases. Formation of cyclic alkene oligomers from back-biting during the ROMP reaction is also known. The reactions reported here are unusual in that they are intermolecular between catalyst and substrate, yet can give 100% yield of product solely from the monomer in the absence of solvent. 13 refs.

  14. Chiral Ketone and Iminium Catalysts for Olefin Epoxidation

    NASA Astrophysics Data System (ADS)

    Wong, O. Andrea; Shi, Yian

    Organo-catalyzed asymmetric epoxidation has received much attention in the past 30 years and significant progress has been made for various types of olefins. This review will cover the advancement made in the field of chiral ketone and chiral iminium salt-catalyzed epoxidations.

  15. Synthesis of all-hydrocarbon stapled α-helical peptides by ring-closing olefin metathesis.

    PubMed

    Kim, Young-Woo; Grossmann, Tom N; Verdine, Gregory L

    2011-06-01

    This protocol provides a detailed procedure for the preparation of stapled α-helical peptides, which have proven their potential as useful molecular probes and as next-generation therapeutics. Two crucial features of this protocol are (i) the construction of peptide substrates containing hindered α-methyl, α-alkenyl amino acids and (ii) the ring-closing olefin metathesis (RCM) of the resulting resin-bound peptide substrates. The stapling systems described in this protocol, namely bridging one or two turns of an α-helix, are highly adaptable to most peptide sequences, resulting in favorable RCM kinetics, helix stabilization and promotion of cellular uptake.

  16. The generation of efficient supported (Heterogeneous) olefin metathesis catalysts

    SciTech Connect

    Grubbs, Robert H

    2013-04-05

    Over the past decade, a new family of homogeneous metathesis catalysts has been developed that will tolerate most organic functionalities as well as water and air. These homogeneous catalysts are finding numerous applications in the pharmaceutical industry as well as in the production of functional polymers. In addition the catalysts are being used to convert seed oils into products that can substitute for those that are now made from petroleum products. Seed oils are unsaturated, contain double bonds, and are a ready source of linear hydrocarbon fragments that are specifically functionalized. To increase the number of applications in the area of biomaterial conversion to petrol chemicals, the activity and efficiency of the catalysts need to be as high as possible. The higher the efficiency of the catalysts, the lower the cost of the conversion and a larger number of practical applications become available. Active supported catalysts were prepared and tested in the conversion of seed oils and other important starting materials. The outcome of the work was successful and the technology has been transferred to a commercial operation to develop viable applications of the discovered systems. A biorefinery that converts seed oils is under construction in Indonesia. The catalysts developed in this study will be considered for the next generation of operations.

  17. Theory-assisted development of a robust and Z-selective olefin metathesis catalyst.

    PubMed

    Occhipinti, Giovanni; Koudriavtsev, Vitali; Törnroos, Karl W; Jensen, Vidar R

    2014-08-07

    DFT calculations have predicted a new, highly Z-selective ruthenium-based olefin metathesis catalyst that is considerably more robust than the recently reported (SIMes)(Cl)(RS)RuCH(o-OiPrC6H4) (3a, SIMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene, R = 2,4,6-triphenylbenzene) [J. Am. Chem. Soc., 2013, 135, 3331]. Replacing the chloride of 3a by an isocyanate ligand to give 5a was predicted to increase the stability of the complex considerably, at the same time moderately improving the Z-selectivity. Compound 5a is easily prepared in a two-step synthesis starting from the Hoveyda-Grubbs second-generation catalyst 3. In agreement with the calculations, the isocyanate-substituted 5a appears to be somewhat more Z-selective than the chloride analogue 3a. More importantly, 5a can be used in air, with unpurified and non-degassed substrates and solvents, and in the presence of acids. These are traits that are unprecedented among highly Z-selective olefin metathesis catalysts and also very promising with respect to applications of the new catalyst.

  18. Liquid-phase synthesis of bridged peptides using olefin metathesis of a protected peptide with a long aliphatic chain anchor.

    PubMed

    Aihara, Keisuke; Komiya, Chiaki; Shigenaga, Akira; Inokuma, Tsubasa; Takahashi, Daisuke; Otaka, Akira

    2015-02-06

    Bridged peptides including stapled peptides are attractive tools for regulating protein-protein interactions (PPIs). An effective synthetic methodology in a heterogeneous system for the preparation of these peptides using olefin metathesis and hydrogenation of protected peptides with a long aliphatic chain anchor is reported.

  19. Characterization and Dynamics of Substituted Ruthenacyclobutanes Relevant to the Olefin Cross-Metathesis Reaction

    PubMed Central

    Blake, Garrett; VanderVelde, David G.; Grubbs, Robert H.

    2011-01-01

    The reaction of the phosphonium alkylidene [(H2IMes)RuCl2=CHP(Cy)3)]+ BF4– with propene, 1-butene, and 1-hexene at –45 °C affords various substituted, metathesis-active ruthenacycles. These metallacycles were found to equilibrate over extended reaction times in response to decreases in ethylene concentrations, which favored increased populations of α-monosubstituted and α,α’-disubstituted (both cis and trans) ruthenacycles. On an NMR timescale, rapid chemical exchange was found to preferentially occur between the β-hydrogens of the cis and trans stereoisomers prior to olefin exchange. Exchange on an NMR timescale was also observed between the α- and β-methylene groups of the monosubstituted ruthenacycle (H2IMes)Cl2Ru(CHRCH2CH2) (R = CH3, CH2CH3, (CH2)3CH3). EXSY NMR experiments at –87 °C were used to determine the activation energies for both of these exchange processes. In addition, new methods have been developed for the direct preparation of metathesis-active ruthenacyclobutanes via the protonolysis of dichloro(1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)(benzylidene) bis(pyridine)ruthenium(II) and its 3-bromopyridine analog. Using either trifluoroacetic acid or silica-bound toluenesulfonic acid as the proton source, the ethylene-derived ruthenacyclobutane (H2IMes)Cl2Ru(CH2CH2CH2) was observed in up to 98% yield via NMR at –40 °C. On the basis of these studies, mechanisms accounting for the positional and stereochemical exchange within ruthenacyclobutanes are proposed, as well as the implications of these dynamics towards olefin metathesis catalyst and reaction design are described. PMID:21452876

  20. Poly(fluoroalkyl acrylate)-bound ruthenium carbene complex: a fluorous and recyclable catalyst for ring-closing olefin metathesis.

    PubMed

    Yao, Qingwei; Zhang, Yiliang

    2004-01-14

    The synthesis of a fluorous olefin metathesis catalyst derived from the Grubbs second-generation ruthenium carbene complex is described. The air stable fluorous polymer-bound ruthenium carbene complex 1 shows high reactivity in effecting the ring-closing metathesis of a broad spectrum of diene and enyne substrates leading to the formation of di-, tri-, and tetrasubstituted cyclic olefins in minimally fluorous solvent systems (PhCF3/CH2Cl2, 1:9-1:49 v/v). The catalyst can be readily separated from the reaction mixture by fluorous extraction with FC-72 and repeatedly reused. The practical advantage offered by the fluorous catalyst is demonstrated by its sequential use in up to five different metathesis reactions.

  1. Development of a Method for the Preparation of Ruthenium Indenylidene-Ether Olefin Metathesis Catalysts

    PubMed Central

    Jimenez, Leonel R.; Tolentino, Daniel R.; Gallon, Benjamin J.; Schrodi, Yann

    2012-01-01

    The reactions between several derivatives of 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and different ruthenium starting materials [i.e., RuCl2(PPh3)3 and RuCl2(pcymene)(L), where L is tricyclohexylphosphine di-t-butylmethylphosphine, dicyclohexylphenylphosphine, triisobutylphosphine, triisopropylphosphine, or tri-npropylphosphine] are described. Several of these reactions allow for the easy, in-situ and atom-economic preparation of olefin metathesis catalysts. Organic precursor 1-(3,5-dimethoxyphenyl)-1-phenyl-prop-2-yn-1-ol led to the formation of active ruthenium indenylidene-ether complexes, while 1-(3,5-dimethoxyphenyl)-prop-2-yn-1-ol and 1-(3,5-dimethoxyphenyl)-1-methyl-prop-2-yn-1-ol did not. It was also found that a bulky and strong σ-donor phosphine ligand was required to impart good catalytic activity to the new ruthenium complexes. PMID:22580400

  2. Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

    PubMed Central

    Pump, Eva; Pazio, Aleksandra E; Woźniak, Krzysztof; Cavallo, Luigi

    2015-01-01

    Summary Two ruthenium olefin metathesis initiators featuring electronically modified quinoline-based chelating carbene ligands are introduced. Their reactivity in RCM and ROMP reactions was tested and the results were compared to those obtained with the parent unsubstituted compound. The studied complexes are very stable at high temperatures up to 140 °C. The placement of an electron-withdrawing functionality translates into an enhanced activity in RCM. While electronically modified precatalysts, which exist predominantly in the trans-dichloro configuration, gave mostly the RCM and a minor amount of the cycloisomerization product, the unmodified congener, which preferentially exists as its cis-dichloro isomer, shows a switched reactivity. The position of the equilibrium between the cis- and the trans-dichloro species was found to be the crucial factor governing the reactivity of the complexes. PMID:26425202

  3. Synthesis of 7-deoxypancratistatin from carbohydrates by the use of olefin metathesis.

    PubMed

    Håkansson, Anders E; Palmelund, Anders; Holm, Henriette; Madsen, Robert

    2006-04-12

    The stereocontrolled synthesis of (+)-7-deoxypancratistatin is described. The convergent synthesis has been achieved by two different strategies, both of which commence from a pentose and piperonal. The latter is converted into allylic bromide 7, which is then coupled with a protected methyl 5-deoxy-5-iodo-D-ribofuranoside in the presence of zinc metal. The first strategy involves a total of only 13 steps from D-ribose and piperonal, but suffers from a low yield in the zinc-mediated reaction between ribofuranoside 9, benzylamine, and bromide 7. The second strategy involves a total of 18 steps from D-xylose and piperonal. The former is converted into ribofuranoside 28, which is coupled with bromide 7 in the presence of zinc, and this is followed by ring-closing olefin metathesis. Subsequent Overman rearrangement, dihydroxylation, and deprotection then affords the natural product.

  4. Tube-in-tube reactor as a useful tool for homo- and heterogeneous olefin metathesis under continuous flow mode.

    PubMed

    Skowerski, Krzysztof; Czarnocki, Stefan J; Knapkiewicz, Paweł

    2014-02-01

    A tube-in-tube reactor was successfully applied in homo- and heterogeneous olefin metathesis reactions under continuous flow mode. It was shown that the efficient removal of ethylene facilitated by connection of the reactor with a vacuum pump significantly improves the outcome of metathesis reactions. The beneficial aspects of this approach are most apparent in reactions performed at low concentration, such as macrocyclization reactions. The established system allows achievement of both improved yield and selectivity, and is ideal for industrial applications. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates: construction of chiral nonracemic allylic isocyanates.

    PubMed

    Grange, Rebecca L; Evans, P Andrew

    2014-08-27

    We report the facile and efficient metal-free metathesis reaction of C-chiral allylic sulfilimines with aryl isocyanates. This process facilitates the room temperature construction of an array of chiral nonracemic allylic isocyanates, which are versatile intermediates for the construction of unsymmetrical ureas, carbamates, thiocarbamates and amides. Furthermore, the sulfilimine/isocyanate metathesis reaction with 4,4'-methylene diphenyl diisocyanate (4,4'-MDI) circumvents harsh reaction conditions and/or hazardous reagents employed with more classical methods for the preparation of this important functional group.

  6. Binary and Ternary Catalytic Systems for Olefin Metathesis Based on MoCl5/SiO2

    NASA Astrophysics Data System (ADS)

    Bykov, Victor I.; Belyaev, Boris A.; Butenko, Tamara A.; Finkelshtein, Eugene Sh.

    Kinetics of α-olefin metathesis in the presence of binary (MoCl5/ SiO2-Me4Sn) and ternary catalytic systems (MoCl5/SiO2-Me4Sn-ECl4, E = Si or Ge) was studied. Specifically, kinetics and reactivity of 1-decene, 1-octene, and 1-hexene in the metathesis reaction at 27°C and 50°C in the presence of MoCl5/ SiO2-SnMe4 were examined and evaluated in detail. It was shown that experimental data comply well with the simple kinetic equation for the rate of formation of symmetrical olefins with allowance for the reverse reaction and catalyst deactivation: r = left( {k_1 \\cdot c_α - k_{ - 1} \\cdot c_s } right) \\cdot e^{ - k_d \\cdot tilde n_{tot} } . The coefficients for this equation were determined, and it was shown that these α-olefins had practically the same reactivity. It was found that reactivation in the course of metathesis took place due to the addition of a third component (silicon tetrachloride or germanium tetrachloride in combination with tetramethyltin) to a partially deactivated catalyst. The number of active centers was determined (5-6% of the amount of Mo) and the mechanisms of formation, deactivation, and reactivation were proposed for the binary and ternary catalytic systems. The role of individual components of the catalytic systems was revealed.

  7. Ruthenium-based olefin metathesis catalysts bearing pH-responsive ligands: External control of catalyst solubility and activity

    NASA Astrophysics Data System (ADS)

    Balof, Shawna Lynn

    2011-12-01

    Sixteen novel, Ru-based olefin metathesis catalysts bearing pH responsive ligands were synthesized. The pH-responsive groups employed with these catalysts included dimethylamino (NMe2) modified NHC ligands as well as N-donor dimethylaminopyridine (DMAP) and 3-(o-pyridyl)propylidene ligands. These pH-responsive ligands provided the means by which the solubility and/or activity profiles of the catalysts produced could be controlled via acid addition. The main goal of this dissertation was to design catalyst systems capable of performing ring opening metathesis (ROMP) and ring closing metathesis (RCM) reactions in both organic and aqueous media. In an effort to quickly gain access to new catalyst structures, a template synthesis for functionalized NHC ligand precursors was designed, in addition to other strategies, to obtain ligand precursors with ancillary NMe2 groups. Kinetic studies for the catalysts produced from these precursors showed external control of catalyst solubility was afforded via protonation of the NMe2 groups of their NHC ligands. Additionally, this protonation afforded external control of catalyst propagation rates for several catalysts. This is the first known independent external control for the propagation rates of ROMP catalysts. The incorporation of pH-responsive N-donor ligands into catalyst structures also provided the means for the external control of metathesis activity, as the protonation of these ligands resulted in an increased initiation rate based on their fast and irreversible dissociation from the metal center. The enhanced external control makes these catalysts applicable to a wide range of applications, some of which have been explored by us and/or through collaboration. Three of the catalysts designed showed remarkable metathesis activity in aqueous media. These catalysts displayed comparable RCM activity in aqueous media to a class of water-soluble catalysts reported by Grubbs et al., considered to be the most active catalyst for

  8. Origins of initiation rate differences in ruthenium olefin metathesis catalysts containing chelating benzylidenes.

    PubMed

    Engle, Keary M; Lu, Gang; Luo, Shao-Xiong; Henling, Lawrence M; Takase, Michael K; Liu, Peng; Houk, K N; Grubbs, Robert H

    2015-05-06

    A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating o-alkoxybenzylidene and the observed initiation rate. Included in this series were previously reported catalysts containing a variety of benzylidene modifications as well as four new catalysts containing cyclopropoxy, neopentyloxy, 1-adamantyloxy, and 2-adamantyloxy groups. The initiation rates of this series of catalysts were determined using a UV/vis assay. All four new catalysts were observed to be faster-initiating than the corresponding isopropoxy control, and the 2-adamantyloxy catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Analysis of the X-ray crystal structures and computed energy-minimized structures of these catalysts revealed no correlation between the Ru-O bond length and Ru-O bond strength. On the other hand, the initiation rate was found to correlate strongly with the computed Ru-O bond strength. This latter finding enables both the rationalization and prediction of catalyst initiation through the calculation of a single thermodynamic parameter in which no assumptions about the mechanism of the initiation step are made.

  9. Evolution of Catalytic Stereoselective Olefin Metathesis: From Ancillary Transformation to Purveyor of Stereochemical Identity

    PubMed Central

    2015-01-01

    There have been numerous significant advances in catalytic olefin metathesis (OM) during the past two decades. Such progress has transformed this important set of reactions to strategically pivotal processes that generate stereochemical identity while delivering molecules that cannot be easily prepared by alternative routes. In this Perspective, an analysis of the origin of the inception of bidentate benzylidene ligands for Ru-based OM catalysts is first presented. This is followed by an overview of the intellectual basis that culminated in the development of Mo-based diolates and stereogenic-at-Ru complexes for enantioselective OM. The principles accrued from the study of the latter Ru carbenes and Mo alkylidenes and utilized in the design of stereogenic-at-Mo, -W, and -Ru species applicable to enantioselective and Z-selective OM are then discussed. The influence of the recently introduced catalytic OM protocols on the design of synthesis routes leading to complex organic molecules is probed. The impact of a better understanding of the mechanistic nuances of OM toward the discovery of stereoselective catalysts is reviewed as well. PMID:24720633

  10. An Electronic Rationale for Observed Initiation Rates in Ruthenium-Mediated Olefin Metathesis: Charge Donation in Phosphine And N-Heterocyclic Carbene Ligands

    SciTech Connect

    Getty, K.; Delgado-Jaime, M.U.; Kennepohl, P.

    2009-06-01

    Ru K-edge XAS data indicate that second generation ruthenium-based olefin metathesis precatalysts (L = N-heterocyclic carbene) possess a more electron-deficient metal center than in the corresponding first generation species (L = tricyclohexylphosphine). This surprising effect is also observed from DFT calculations and provides a simple rationale for the slow phosphine dissociation kinetics previously noted for second-generation metathesis precatalysts.

  11. Introduction of all-hydrocarbon i,i+3 staples into alpha-helices via ring-closing olefin metathesis.

    PubMed

    Kim, Young-Woo; Kutchukian, Peter S; Verdine, Gregory L

    2010-07-02

    The introduction of all-hydrocarbon i,i+3 staples into alpha-helical peptide scaffolds via ring-closing olefin metathesis (RCM) between two alpha-methyl,alpha-pentenylglycine residues incorporated at i and i+3 positions, which lie on the same face of the helix, has been investigated. The reactions were found to be highly dependent upon the side-chain stereochemistry of the amino acids undergoing RCM. The i,i+3 stapling system established here provides a potentially useful alternative to the well-established i,i+4 stapling system now in widespread use.

  12. Evolution of a total synthesis of (-)-kendomycin exploiting a Petasis-Ferrier rearrangement/ring-closing olefin metathesis strategy.

    PubMed

    Smith, Amos B; Mesaros, Eugen F; Meyer, Emmanuel A

    2006-04-19

    A convergent stereocontrolled total synthesis of (-)-kendomycin (1) has been achieved. The synthesis proceeds with a longest linear sequence of 21 steps, beginning with commercially available 2,4-dimethoxy-3-methylbenzaldehyde (12). Highlights of the synthesis include an effective Petasis-Ferrier union/rearrangement tactic to construct the sterically encumbered tetrahydropyran ring, a ring-closing metathesis to generate the C(4a-13-20a) macrocycle, an effective epoxidation/deoxygenation sequence to isomerize the C(13,14) olefin, and a biomimetic quinone-methide-lactol assembly to complete the synthesis.

  13. Cycloalkyl-based unsymmetrical unsaturated (U₂)-NHC ligands: flexibility and dissymmetry in ruthenium-catalysed olefin metathesis.

    PubMed

    Rouen, Mathieu; Borré, Etienne; Falivene, Laura; Toupet, Loic; Berthod, Mikaël; Cavallo, Luigi; Olivier-Bourbigou, Hélène; Mauduit, Marc

    2014-05-21

    Air-stable Ru-indenylidene and Hoveyda-type complexes bearing new unsymmetrical unsaturated N-heterocyclic carbene (U2-NHC) ligands combining a mesityl unit and a flexible cycloalkyl moiety as N-substituents were synthesised. Structural features, chemical stabilities and catalytic profiles in olefin metathesis of this new library of cycloalkyl-based U2-NHC Ru complexes were studied and compared with their unsymmetrical saturated NHC-Ru homologues as well as a set of commercially available Ru-catalysts bearing either symmetrical SIMes or IMes NHC ligands.

  14. An S(N)Ar approach to sterically hindered ortho-alkoxybenzaldehydes for the synthesis of olefin metathesis catalysts.

    PubMed

    Engle, Keary M; Luo, Shao-Xiong; Grubbs, Robert H

    2015-04-17

    A three-step procedure has been developed for preparing ortho-alkoxybenzaldehydes from ortho-fluorobenzaldehydes that tolerates the use of sterically hindered sodium alkoxide nucleophiles. The protocol is modular and operationally convenient. The ortho-alkoxybenzaldehyde products can be converted in one additional step to ortho-alkoxystyrenes by a Wittig reaction. These styrenes are precursors to the chelating benzylidene moiety in a proposed series of novel ruthenium complexes for use in olefin metathesis. Chelation with three representative styrenes has been demonstrated.

  15. Diastereoselective aziridination of chiral electron-deficient olefins with N-chloro-N-sodiocarbamates catalyzed by chiral quaternary ammonium salts.

    PubMed

    Murakami, Yuta; Takeda, Youhei; Minakata, Satoshi

    2011-08-05

    Chiral quaternary ammonium salt-catalyzed diastereoselective aziridination of electron-deficient olefins that possess a chiral auxiliary with N-chloro-N-sodiocarbamates was developed. The key to high stereoselectivity was found to be the employment of the "matching" stereochemical combination of chiral auxiliary/ammonium salt. For example, when 3-phenyl-(4R,7S)-4-methyl-7-isopropyl-4,5,6,7-tetrahydroindazole (L-menthopyrazole) as a chiral auxiliary and a cinchonidine-derived chiral ammonium salt as a catalyst were applied to the reaction system, perfect diastereoselectivity was realized. Furthermore, the preparation of enantiomerically pure aziridines by removal of the chiral auxiliary was demonstrated.

  16. Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

    ERIC Educational Resources Information Center

    Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

    2007-01-01

    A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

  17. Rationalizing current strategies to protect N-heterocyclic carbene-based ruthenium catalysts active in olefin metathesis from C-H (de)activation.

    PubMed

    Poater, Albert; Bahri-Laleh, Naeimeh; Cavallo, Luigi

    2011-06-21

    Defending second generation Ru-catalysts in olefin metathesis from C-H (de)activation reactions requires precise catalyst design strategies. Computer simulations are used here to rationalize precisely the role of the currently used catalyst structural modifications, and the way these modifications cooperate.

  18. Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

    ERIC Educational Resources Information Center

    Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

    2007-01-01

    A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

  19. Ligand Exchange-Mediated Activation and Stabilization of a Re-Based Olefin Metathesis Catalyst by Chlorinated Alumina.

    PubMed

    Gallo, Alessandro; Fong, Anthony; Szeto, Kai C; Rieb, Julia; Delevoye, Laurent; Gauvin, Régis M; Taoufik, Mostafa; Peters, Baron; Scott, Susannah L

    2016-10-05

    Extensive chlorination of γ-Al2O3 results in the formation of highly Lewis acidic surface domains depleted in surface hydroxyl groups. Adsorption of methyltrioxorhenium (MTO) onto these chlorinated domains serves to activate it as a low temperature, heterogeneous olefin metathesis catalyst and confers both high activity and high stability. Characterization of the catalyst reveals that the immobilized MTO undergoes partial ligand exchange with the surface, whereby some Re sites acquire a chloride ligand from the modified alumina while donating an oxo ligand to the support. More specifically, Re LIII-edge EXAFS and DFT calculations support facile ligand exchange between MTO and Cl-Al2O3 to generate [CH3ReO2Cl(+)] fragments that interact with a bridging oxygen of the support via a Lewis acid-base interaction. According to IR and solid-state NMR, the methyl group remains intact, and does not evolve spontaneously to a stable methylene tautomer. Nevertheless, the chloride-promoted metathesis catalyst is far more active and productive than MTO/γ-Al2O3, easily achieving a TON of 100 000 for propene metathesis in a flow reactor at 10 °C (compared to TON < 5000 for the nonchlorinated catalyst). Increased activity is a consequence of both a larger fraction of active sites and a higher intrinsic activity for the new sites. Increased stability is tentatively attributed to a stronger interaction between MTO and chlorinated surface regions, as well as extensive depletion of the Brønsted acidic surface hydroxyl population. The reformulated catalyst represents a major advance for Re-based metathesis catalysts, whose widespread use has thus far been severely hampered by their instability.

  20. Kinetic resolution of planar-chiral 1,2-disubstituted ferrocenes by molybdenum-catalyzed asymmetric intraannular ring-closing metathesis.

    PubMed

    Ogasawara, Masamichi; Arae, Sachie; Watanabe, Susumu; Nakajima, Kiyohiko; Takahashi, Tamotsu

    2013-03-25

    Planar chirality: Ring-closing metathesis of 1,2-diallylmetallocenes afforded the corresponding 4,7-dihydroindenyl species in high yields. The metallocenes are planar chiral with two different allylic substituents, and kinetic resolution of the racemic 1,2-diallylmetallocene derivatives was realized by molybdenum-catalyzed asymmetric ring-closing metathesis with excellent enantioselectivity (see scheme).

  1. High selectivity production of propylene from 2-butene: non-degenerate pathways to convert symmetric olefins via olefin metathesis.

    PubMed

    Mazoyer, Etienne; Szeto, Kai C; Basset, Jean-Marie; Nicholas, Christopher P; Taoufik, Mostafa

    2012-04-14

    The first example of propylene production from 2-butene in promising yield is described by reacting trans-2-butene over tungsten hydrides precursor W-H/Al(2)O(3) at 150 °C and different pressures in a continuous flow reactor. The tungsten carbene-hydride active site operates as a "bi-functional catalyst" through the disfavoured 2-butene isomerisation on W-hydride and 2-butenes/1-butene cross-metathesis on W-carbene.

  2. Orthogonal ring-closing alkyne and olefin metathesis for the synthesis of small GTPase-targeting bicyclic peptides

    PubMed Central

    Cromm, Philipp M.; Schaubach, Sebastian; Spiegel, Jochen; Fürstner, Alois; Grossmann, Tom N.; Waldmann, Herbert

    2016-01-01

    Bicyclic peptides are promising scaffolds for the development of inhibitors of biological targets that proved intractable by typical small molecules. So far, access to bioactive bicyclic peptide architectures is limited due to a lack of appropriate orthogonal ring-closing reactions. Here, we report chemically orthogonal ring-closing olefin (RCM) and alkyne metathesis (RCAM), which enable an efficient chemo- and regioselective synthesis of complex bicyclic peptide scaffolds with variable macrocycle geometries. We also demonstrate that the formed alkyne macrocycle can be functionalized subsequently. The orthogonal RCM/RCAM system was successfully used to evolve a monocyclic peptide inhibitor of the small GTPase Rab8 into a bicyclic ligand. This modified peptide shows the highest affinity for an activated Rab GTPase that has been reported so far. The RCM/RCAM-based formation of bicyclic peptides provides novel opportunities for the design of bioactive scaffolds suitable for the modulation of challenging protein targets. PMID:27075966

  3. A two-color fluorogenic carbene complex for tagging olefins via metathesis reaction

    NASA Astrophysics Data System (ADS)

    Wirtz, Marcel; Grüter, Andreas; Heib, Florian; Huch, Volker; Zapp, Josef; Herten, Dirk-Peter; Schmitt, Michael; Jung, Gregor

    2015-12-01

    We describe a fluorogenic ruthenium (II) carbene complex in which the chromophore is directly connected to the metal center. The compound introduces a boron dipyrromethene (BODIPY) moiety into target double bonds by metathesis. Tagging of terminal double bonds is demonstrated on immobilized styrene units on a glass surface. We also show that two compounds with distinguishable fluorescence properties are formed in the model reaction with styrene. The outcome of the metathesis reaction is characterized by 19F-NMR, optical spectroscopy, and, finally, single-molecule trajectories. This labeling scheme, in our perception, is of particular interest in the fields of interfacial science and biorthogonal ligation in combination with super-resolution imaging.

  4. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis

    ERIC Educational Resources Information Center

    Casey, Charles P.

    2006-01-01

    The 2005 Nobel Prize in Chemistry was awarded "for the development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other…

  5. 2005 Nobel Prize in Chemistry: Development of the Olefin Metathesis Method in Organic Synthesis

    ERIC Educational Resources Information Center

    Casey, Charles P.

    2006-01-01

    The 2005 Nobel Prize in Chemistry was awarded "for the development of the metathesis method in organic synthesis". The discoveries of the laureates provided a chemical reaction used daily in the chemical industry for the efficient and more environmentally friendly production of important pharmaceuticals, fuels, synthetic fibers, and many other…

  6. Glycosyl-Templated Chiral Helix Stapling of Ethynylpyridine Oligomers by Alkene Metathesis between Inter-Pitch Side Chains.

    PubMed

    Abe, Hajime; Kayamori, Fumihiro; Inouye, Masahiko

    2015-06-22

    Ethynylpyridine polymers and oligomers consisting of 4-substituted pyridine rings linked by acetylene bonds at the 2- and 6-positions have been investigated. Ethynylpyridine oligomers covalently linked with a glycosyl chiral template form chiral helical complexes by intramolecular hydrogen bonding, in which the chirality of the template is translated to the helix. With a view to fixation of the chiral architecture, D/L-galactosyl- and D/L-mannosyl-linked ethynylpyridine oligomers have been developed with 4-(3-butenyloxy)pyridine units having alkene side chains. The helical structures are successfully stapled by alkene metathesis of the side chains. Subsequent removal of the chiral templates by acidolysis produces template-free stapled oligomers. The chiral, template-free, stapled oligomers show chiral helicity, which is resistant to polar solvents and heating.

  7. Shell Higher Olefins Process.

    ERIC Educational Resources Information Center

    Lutz, E. F.

    1986-01-01

    Shows how olefin isomerization and the exotic olefin metathesis reaction can be harnessed in industrial processes. Indicates that the Shell Higher Olefins Process makes use of organometallic catalysts to manufacture alpha-olefins and internal carbon-11 through carbon-14 alkenes in a flexible fashion that can be adjusted to market needs. (JN)

  8. Shell Higher Olefins Process.

    ERIC Educational Resources Information Center

    Lutz, E. F.

    1986-01-01

    Shows how olefin isomerization and the exotic olefin metathesis reaction can be harnessed in industrial processes. Indicates that the Shell Higher Olefins Process makes use of organometallic catalysts to manufacture alpha-olefins and internal carbon-11 through carbon-14 alkenes in a flexible fashion that can be adjusted to market needs. (JN)

  9. A Well-Defined, Silica-Supported Tungsten Imido Alkylidene OlefinMetathesis Catalyst

    SciTech Connect

    Rhers, Bochra; Salameh, Alain; Baudouin, Anne; Quadrelli, ElsjeA.; Taoufik, Mostafa; Coperet, Christophe; Lefebvre, Frederic; Basset,Jean-Marie; Solans-Monfort, Xavier; Eisenstein, Odile; Lukens, Wayne W.; Lopez, Lordes.P.H.; Sinha, Amritanshu; Schrock, Richard R.

    2006-06-13

    The reaction of [W(=NAr)(=CHtBu)(CH2tBu)2](1; Ar =2,6-iPrC6H3) with a silica partially dehydroxylated at 700oC, SiO2-(700),gives syn-[(_SiO)W(=NAr)(=CHtBu)(CH2tBu)](2) as a major surface species,which was fully characterized by mass balance analysis, IR, NMR, EXAFS,and DFT periodic calculations. Similarly, complex 1 reacts with[(c-C5H9)7Si7O12SiOH]to give [(SiO)W(=NAr)(=CHtBu)(CH2tBu)](2m), whichshows similar spectroscopic properties. Surface complex 2 is a highlyactive propene metathesis catalyst, which can achieve a TON of 16000within 100 h, with only a slow deactivation.

  10. Olefin metathesis and quadruple hydrogen bonding: A powerful combination in multistep supramolecular synthesis

    PubMed Central

    Scherman, Oren A.; Ligthart, G. B. W. L.; Ohkawa, Haruki; Sijbesma, Rint P.; Meijer, E. W.

    2006-01-01

    We show that combining concepts generally used in covalent organic synthesis such as retrosynthetic analysis and the use of protecting groups, and applying them to the self-assembly of polymeric building blocks in multiple steps, results in a powerful strategy for the self-assembly of dynamic materials with a high level of architectural control. We present a highly efficient synthesis of bifunctional telechelic polymers by ring-opening metathesis polymerization (ROMP) with complementary quadruple hydrogen-bonding motifs. Because the degree of functionality for the polymers is 2.0, the formation of alternating, blocky copolymers was demonstrated in both solution and the bulk leading to stable, microphase-separated copolymer morphologies. PMID:16877543

  11. Chiral Cu(salen)-Based Metal-Organic Framework for Heterogeneously Catalyzed Aziridination and Amination of Olefins.

    PubMed

    Liu, Yan; Li, Zijian; Yuan, Guozan; Xia, Qingchun; Yuan, Chen; Cui, Yong

    2016-12-19

    A homochiral 3D porous metal-organic framework was assembled from a chiral dicarboxylic acid-functionalized Cu(salen)-based catalyst and could serve as an efficient heterogeneous catalyst for aziridination and allylic amination of olefins. Besides easy separation and reuse of the catalyst, the chiral framework confinement could impart substrate size selectivity, enhance catalyst activity, and induce product enantioselectivity.

  12. Z-Selective Olefin Metathesis Reactions Promoted by Tungsten Oxo Alkylidene Complexes

    PubMed Central

    Peryshkov, Dmitry V.; Schrock, Richard R.; Takase, Michael K.; Müller, Peter; Hoveyda, Amir H.

    2011-01-01

    Addition of LiOHMT (OHMT = O-2,6-dimesitylphenoxide) to W(O)(CH-t-Bu)(PMe2Ph)2Cl2 led to WO(CH-t-Bu)Cl(OHMT)(PMe2Ph) (4). Subsequent addition of Li(2,5-Me2C4H2N) to 4 yielded yellow W(O)(CH-t-Bu)(OHMT)(Me2Pyr)(PMe2Ph) (5). Compound 5 is a highly effective catalyst for the Z-selective coupling of selected terminal olefins (at 0.2% loading) to give product in >75% yield with >99% Z configuration. Addition of two equivalents of B(C6F5)3 to 5 led to catalyst activated at the oxo ligand by B(C6F5)3. 5.B(C6F5)3 is a highly active catalyst that produces thermodynamic products (~20% Z). PMID:22107254

  13. Self-healing polymers---The importance of choosing an adequate healing monomer, and the olefin metathesis polymerization of agricultural oils

    NASA Astrophysics Data System (ADS)

    Mauldin, Timothy C.

    Modern society's immense and ill-fated reliance on petrochemical-based polymeric materials will likely necessitate a shift in polymer production paradigms in the near future. The work presented herein attempts to address this issue via a two-pronged approach. First, efforts to improve the duration of composite materials by incorporation of a self-healing function are discussed, the fruitful application of which can potentially reduce or eliminate the massive carbon footprints associated with the repair/replacement of damaged materials. And second, polymeric materials derived predominately from natural and renewable feedstock---namely vegetable oils---are developed. Early microcapsule-based self-healing materials utilized dicyclopentadiene-filled microcapsules and Grubbs' olefin metathesis catalyst to initiate the healing mechanism. However, the patent-protected catalyst, made from the precious metal ruthenium and sometimes costly ligands, will likely never be inexpensive and therefore limit large-scale applications. Hence, clever approaches to reduce the healing catalyst loading in self-healing polymers are of great interest. To this end, our efforts have revolved around solving the problem of the relatively inefficient use of Grubbs' catalyst during the healing mechanism. Given that the mismatch of the olefin metathesis polymerization and Grubbs' catalyst dissolution (in monomer) kinetics is a known cause of this inefficient use of the catalyst, we attempted to tune the "latency" (i.e. pot life) of the olefin metathesis polymerization to ensure more complete dissolution of catalyst in monomer. In an alternative approach to improving efficient catalyst dissolution, we developed a simple model to predict relative dissolution rates of Grubbs' catalyst in a small library of healing monomers. This model was shown experimentally to be able to aid in the selection of, for example, reactive monomer additives that can yield impressive improvements in catalyst dissolution

  14. Ring-expanding olefin metathesis: a route to highly active unsymmetrical macrocyclic oligomeric co-salen catalysts for the hydrolytic kinetic resolution of epoxides.

    PubMed

    Zheng, Xiaolai; Jones, Christopher W; Weck, Marcus

    2007-02-07

    In the presence of the third generation Grubbs catalyst, the ring-expanding olefin metathesis of a monocyclooct-4-en-1-yl functionalized salen ligand and the corresponding Co(II)(salen) complex at low monomer concentrations results in the exclusive formation of macrocyclic oligomeric structures with the salen moieties being attached in an unsymmetrical, flexible, pendent manner. The TOF-MALDI mass spectrometry reveals that the resulting macrocyclic oligomers consist predominantly of dimeric to tetrameric species, with detectable traces of higher homologues up to a decamer. Upon activation under aerobic and acidic conditions, these Co(salen) macrocycles exhibit extremely high reactivities and selectivities in the hydrolytic kinetic resolution (HKR) of a variety of racemic terminal epoxides under neat conditions with very low catalyst loadings. The excellent catalytic properties can be explained in terms of the new catalyst's appealing structural features, namely, the flexible oligomer backbone, the unsymmetrical pendent immobilization motif of the catalytic sites, and the high local concentration of Co(salen) species resulting from the macrocyclic framework. This ring-expanding olefin metathesis is suggested to be a simple way to prepare tethered metal complexes that are endowed with key features--(i) a high local concentration of metal complexes and (ii) a flexible, single point of attachment to the support--that facilitate rapid and efficient catalysis when a bimetallic transition state is required.

  15. Activation of Surface ReO x Sites on Al 2 O 3 Catalysts for Olefin Metathesis

    SciTech Connect

    Lwin, Soe; Li, Yuanyuan; Frenkel, Anatoly I.; Wachs, Israel E.

    2015-11-06

    The nature of activated surface ReOx sites and surface reaction intermediates for supported ReOx/Al2O3 catalysts during propylene self-metathesis were systematically investigated for the first time using in situ spectroscopy (Raman, UV–vis, XAS (XANES/EXAFS) and IR). In situ Raman spectroscopy reveals that olefins selectively interact with the surface dioxo ReO4 sites anchored at acidic alumina hydroxyls. In situ UV–vis indicates that surface Re5+ and some Re6+ sites form, and in situ XAS indicates a reduction in the number of Re=O bond character in the propylene self-metathesis reaction environment, especially as the temperature is increased. The appearance of oxygenated products during propylene activation supports the conclusion that catalyst activation involves removal of oxygen from the surface rhenia sites (pseudo-Wittig mechanism). Isotopic CD3CD=CD2 → CH3CH=CH2 switch experiments demonstrate the presence of surface Re=CD2 and Re=CDCD3 reaction intermediates, with the surface Re=CD2 species being the most abundant reaction intermediate. In situ IR spectroscopy indicates the presence of significant surface propylene π complexes on alumina and rhenia sites of the catalyst, which complicates analysis of surface reaction intermediates during propylene self-metathesis.

  16. A fast-initiating ionically tagged ruthenium complex: a robust supported pre-catalyst for batch-process and continuous-flow olefin metathesis.

    PubMed

    Borré, Etienne; Rouen, Mathieu; Laurent, Isabelle; Magrez, Magaly; Caijo, Fréderic; Crévisy, Christophe; Solodenko, Wladimir; Toupet, Loic; Frankfurter, René; Vogt, Carla; Kirschning, Andreas; Mauduit, Marc

    2012-12-14

    In this study, a new pyridinium-tagged Ru complex was designed and anchored onto sulfonated silica, thereby forming a robust and highly active supported olefin-metathesis pre-catalyst for applications under batch and continuous-flow conditions. The involvement of an oxazine-benzylidene ligand allowed the reactivity of the formed Ru pre-catalyst to be efficiently controlled through both steric and electronic activation. The oxazine scaffold facilitated the introduction of the pyridinium tag, thereby affording the corresponding cationic pre-catalyst in good yield. Excellent activities in ring-closing (RCM), cross (CM), and enyne metathesis were observed with only 0.5 mol % loading of the pre-catalyst. When this powerful pre-catalyst was immobilized onto a silica-based cationic-exchange resin, a versatile catalytically active material for batch reactions was generated that also served as fixed-bed material for flow reactors. This system could be reused at 1 mol % loading to afford metathesis products in high purity with very low ruthenium contamination under batch conditions (below 5 ppm). Scavenging procedures for both batch and flow processes were conducted, which led to a lowering of the ruthenium content to as little as one tenth of the original values. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters.

    PubMed

    Benedetti, Fabio; Berti, Federico; Fanfoni, Lidia; Garbo, Michele; Regini, Giorgia; Felluga, Fulvia

    2016-06-21

    The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral β-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

  18. Tandem catalysis in domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization: concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives.

    PubMed

    Fuwa, Haruhiko; Noguchi, Takuma; Noto, Kenkichi; Sasaki, Makoto

    2012-10-28

    Herein, we describe the concise synthesis of 2,6-cis-substituted tetrahydropyran derivatives based on a domino olefin cross-metathesis/intramolecular oxa-conjugate cyclization (CM/IOCC) reaction. We have found that the domino CM/IOCC of δ-hydroxy olefins with α,β-unsaturated carbonyl compounds (e.g., trans-crotonaldehyde or N-acryloyl-2,5-dimethylpyrrole) could be efficiently achieved in the presence of the second-generation Hoveyda-Grubbs catalyst under elevated temperature conditions, directly affording 2,6-cis-substituted tetrahydropyrans in excellent yields with synthetically useful diastereoselectivity ("auto-tandem catalysis"). In addition, we have found that the domino CM/IOCC of δ-hydroxy olefins with α,β-unsaturated carbonyl compounds could be achieved simply by performing CM in the presence of a Brønsted acid in CH(2)Cl(2) at 25-35 °C, which delivered 2,6-cis-substituted tetrahydropyrans in good yields with excellent diastereoselectivity ("orthogonal-tandem catalysis"). To understand the mechanism of auto-tandem catalysis in the domino CM/IOCC reaction, we have investigated the role of ruthenium hydride complexes in the IOCC of a ζ-hydroxy α,β-unsaturated ketone as a model case.

  19. 1-O-vinyl glycosides via Tebbe olefination, their use as chiral auxiliaries and monomers.

    PubMed

    Yuan, Jialong; Lindner, Kristof; Frauenrath, Holger

    2006-07-21

    A series of anomerically pure 1-O-formyl glycosides 1 was prepared and converted into the corresponding 1-O-vinyl glycosides 2 by Tebbe olefination. The unsubstituted vinyl glycosides were obtained as anomerically pure compounds in good yields, and the method of preparation was compatible with the presence of a variety of functional groups. Remarkably, the anomeric formate group was regioselectively converted into the corresponding olefin in the presence of acetate and benzoate protecting groups. With the perspective to use the 1-O-vinyl glycosides as monomers for the preparation of glycosylated poly(vinyl alcohol) derivatives with controlled tacticity, their scope as chiral auxiliaries for a stereodifferentiation in addition reactions to the olefin function was investigated by using the [2+2] cycloaddition to dichloroketene as a model reaction. In particular, vinyl 2,3,4,6-tetra-O-benzoyl-alpha-d-mannopyranoside (2i) exhibited excellent diastereoselectivity. Finally, the 1-O-vinyl glycosides were successfully subjected to radical homopolymerization in bulk or used as electron-rich comonomers in radical copolymerizations with maleic anhydride, yielding alternating, glycosylated poly(vinyl alcohol-alt-maleic anhydride).

  20. Ruthenium—Arene Complexes Derived from NHC•CO2 and NHC•CS2 Zwitterionic Adducts and Their Use in Olefin Metathesis

    NASA Astrophysics Data System (ADS)

    Delaude, Lionel; Demonceau, Albert

    A range of imidazol(in)ium-2-carboxylates and -dithiocarboxylates bearing alkyl or aryl groups on their nitrogen atoms were prepared by reacting the corresponding N-heterocyclic carbenes (NHCs) with either carbon dioxide or carbon disulfide. All the zwitterionic products were characterized by various analytical techniques, including thermogravimetric analysis (TGA). Their ability to act as NHC ligand precursors for in situ catalytic applications was investigated in the ruthenium-promoted ring-opening metathesis polymerization (ROMP) of cyclo-octene. Upon exposure to the [RuCl2(p-cymene)]2 dimer, the NHC CO2 adducts readily dissociated to generate [RuCl2(p-cymene)(NHC)] complexes that were highly active catalyst precursors for olefin metathesis. Conversely, the NHC CS2 betaines retained their zwitterionic nature and led to new cationic complexes of the [RuCl(p-cymene)(NHC CS2)]+PF6 - type that were devoid of any significant catalytic activity in the reaction under consideration

  1. Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products

    PubMed Central

    Kunz, Oliver

    2013-01-01

    Summary Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru–lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation. PMID:24367418

  2. Asymmetric synthesis of axially chiral anilides by Pd-catalyzed allylic substitutions with P/olefin ligands.

    PubMed

    Liu, Yilin; Feng, Xiangqing; Du, Haifeng

    2015-01-07

    As an attractive class of non-biaryl atropisomeric compounds, C-N axially chiral anilides have received considerable attention, and several methods have been successfully developed for their synthesis. Pd-catalyzed asymmetric allylic amination was proved to be an effective approach for the chiral anilide synthesis, although only moderate enantioselectivity and relatively narrow substrate scope have been achieved in the previous work. Searching for highly efficient methods for the synthesis of axially chiral anilides is therefore of great interest in synthetic and pharmaceutical chemistry. In this paper, a palladium-catalyzed asymmetric allylic substitution of ortho-substituted anilides using phosphorus amidite-olefin ligands was successfully achieved to afford a variety of axially chiral anilides in high yields with up to 84% ee. The absolute configurations of chiral anilides were also determined from X-ray and CD spectra.

  3. Carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins: highly enantioselective and chemoselective access to a chiral benzylmethyl center.

    PubMed

    Yang, Shuang; Zhu, Shou-Fei; Guo, Na; Song, Song; Zhou, Qi-Lin

    2014-04-07

    A carboxy-directed asymmetric hydrogenation of α-alkyl-α-aryl terminal olefins was developed by using a chiral spiro iridium catalyst, providing a highly efficient approach to the compounds with a chiral benzylmethyl center. The carboxy-directed hydrogenation prohibited the isomerization of the terminal olefins, and realized the chemoselective hydrogenation of various dienes. The concise enantioselective syntheses of (S)-curcudiol and (S)-curcumene were achieved by using this catalytic asymmetric hydrogenation as a key step.

  4. Grubbs–Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids

    PubMed Central

    Koy, Maximilian; Altmann, Hagen J; Autenrieth, Benjamin; Frey, Wolfgang

    2015-01-01

    Summary The novel dicationic metathesis catalyst [(RuCl2(H2ITapMe2)(=CH–2-(2-PrO)-C6H4))2+ (OTf−)2] (Ru-2, H2ITapMe2 = 1,3-bis(2’,6’-dimethyl-4’-trimethylammoniumphenyl)-4,5-dihydroimidazol-2-ylidene, OTf− = CF3SO3 −) based on a dicationic N-heterocyclic carbene (NHC) ligand was prepared. The reactivity was tested in ring opening metathesis polymerization (ROMP) under biphasic conditions using a nonpolar organic solvent (toluene) and the ionic liquid (IL) 1-butyl-2,3-dimethylimidazolium tetrafluoroborate [BDMIM+][BF4 −]. The structure of Ru-2 was confirmed by single crystal X-ray analysis. PMID:26664582

  5. A Procedure Identifying a Polyacetylene Initiator of Olefin Metathesis. The Reactivities of Metal-Carbenes Toward Alkenes and Alkynes.

    DTIC Science & Technology

    2014-09-26

    other evidence was sought that would bear on the hypothesis. The following more stringent test was therefore designed: since the initiator of olefin...Stojanov, C. Kaut. Gummi Kunstst. 1968, 21, 609. (d) Lloyd, D. R. J. Lig. Chromatogr. 1980, 3, 1111. .. . . . . . . . .. -29- (9) (a) Mayo, F. R. J. Am. Chem

  6. Cationic bis-N-heterocyclic carbene (NHC) ruthenium complex: structure and application as latent catalyst in olefin metathesis.

    PubMed

    Rouen, Mathieu; Queval, Pierre; Falivene, Laura; Allard, Jessica; Toupet, Loïc; Crévisy, Christophe; Caijo, Frédéric; Baslé, Olivier; Cavallo, Luigi; Mauduit, Marc

    2014-10-13

    An unexpected cationic bis-N-heterocyclic carbene (NHC) benzylidene ether based ruthenium complex (2 a) was prepared through the double incorporation of an unsymmetrical unsaturated N-heterocyclic carbene (U2 -NHC) ligand that bore an N-substituted cyclododecyl side chain. The isolation and full characterization (including X-ray diffraction studies) of key synthetic intermediates along with theoretical calculations allowed us to understand the mechanism of the overall cationization process. Finally, the newly developed complex 2 a displayed interesting latent behavior during ring-closing metathesis, which could be "switched on" under acidic conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Carboxylate-Assisted C(sp3)–H Activation in Olefin Metathesis-Relevant Ruthenium Complexes

    PubMed Central

    2015-01-01

    The mechanism of C–H activation at metathesis-relevant ruthenium(II) benzylidene complexes was studied both experimentally and computationally. Synthesis of a ruthenium dicarboxylate at a low temperature allowed for direct observation of the C–H activation step, independent of the initial anionic ligand-exchange reactions. A first-order reaction supports an intramolecular concerted metalation–deprotonation mechanism with ΔG⧧298K = 22.2 ± 0.1 kcal·mol–1 for the parent N-adamantyl-N′-mesityl complex. An experimentally determined ΔS⧧ = −5.2 ± 2.6 eu supports a highly ordered transition state for carboxylate-assisted C(sp3)–H activation. Experimental results, including measurement of a large primary kinetic isotope effect (kH/kD = 8.1 ± 1.7), agree closely with a computed six-membered carboxylate-assisted C–H activation mechanism where the deprotonating carboxylate adopts a pseudo-apical geometry, displacing the aryl ether chelate. The rate of cyclometalation was found to be influenced by both the electronics of the assisting carboxylate and the ruthenium ligand environment. PMID:24731019

  8. Recent Applications of Alkene Metathesis in Fine Chemical Synthesis

    NASA Astrophysics Data System (ADS)

    Bicchielli, Dario; Borguet, Yannick; Delaude, Lionel; Demonceau, Albert; Dragutan, Ileana; Dragutan, Valerian; Jossifov, Christo; Kalinova, Radostina; Nicks, François; Sauvage, Xavier

    During the last decade or so, the emergence of the metathesis reaction in organic synthesis has revolutionised the strategies used for the construction of complex molecular structures. Olefin metathesis is indeed particularly suited for the construction of small open-chain molecules and macrocycles using crossmetathesis and ring-closing metathesis, respectively. These reactions serve, inter alia, as key steps in the synthesis of various agrochemicals and pharmaceuticals such as macrocyclic peptides, cyclic sulfonamides, novel macrolides, or insect pheromones. The present chapter is aiming at illustrating the great synthetic potential of metathesis reactions. Shortcomings, such as the control of olefin geometry and the unpredictable effect of substituents on the reacting olefins, will also be addressed. Examples to be presented include epothilones, amphidinolides, spirofungin A, and archazolid. Synthetic approaches involving silicon-tethered ring-closing metathesis, relay ring-closing metathesis, sequential reactions, domino as well as tandem metathesis reactions will also be illustrated.

  9. Planar-Chiral Phosphine-Olefin Ligands Exploiting a (Cyclopentadienyl)manganese(I) Scaffold To Achieve High Robustness and High Enantioselectivity.

    PubMed

    Kamikawa, Ken; Tseng, Ya-Yi; Jian, Jia-Hong; Takahashi, Tamotsu; Ogasawara, Masamichi

    2017-02-01

    A series of 2-methyl-1,3-propenylene-bridged (η(5)-diarylphosphinocyclopentadienyl)(phosphine)manganese(I) dicarbonyl complexes 2 have been developed as a new class of phosphine-olefin ligands based on a planar-chiral transition-metal scaffold, which show better robustness as well as higher enantioselectivity over phosphine-olefin ligands 1 with a planar-chiral (η(6)-arene)chromium(0) framework. The practical enantiospecific and scalable synthesis of 2 has been established. Phosphine-olefin ligands 2 enable construction of an effective chiral environment around a transition-metal center upon coordination, and thus their rhodium(I) complexes exhibit excellent catalytic performance in the various asymmetric addition reactions of arylboron nucleophiles. Complex 2b, which has a bis(3,5-dimethylphenyl)phosphino group on the cyclopentadienyl ring, is found to be a superior chiral ligand in the rhodium-catalyzed asymmetric 1,4-addition reactions of arylboronic acids to various cyclic/acyclic enones giving the corresponding arylation products in over 99% ee. On the other hand, 2c and 2d, which have bis[3,5-bis(trifluoromethyl)phenyl]phosphino and bis(3,5-di-tert-buthyl-4-methoxyphenyl)phosphino groups, respectively, are highly efficient chiral ligands in the rhodium-catalyzed asymmetric 1,2-addition reactions of the arylboron nucleophiles to imines or aldehydes showing up to 99.9% ee. The X-ray crystallographic studies of (R)-2b and [RhCl((S*)-2b)]2 reveal the absolute configuration of 2b and its phosphine-olefin bidentate coordination to a rhodium(I) cation. Structural comparison with [RhCl((R*)-1b)]2 postulates the origins of the higher enantioselectivity of newly developed phosphine-olefin ligands 2.

  10. Alkene Metathesis and Renewable Materials: Selective Transformations of Plant Oils

    NASA Astrophysics Data System (ADS)

    Malacea, Raluca; Dixneuf, Pierre H.

    The olefin metathesis of natural oils and fats and their derivatives is the basis of clean catalytic reactions relevant to green chemistry processes and the production of generate useful chemicals from renewable raw materials. Three variants of alkene metathesis: self-metathesis, ethenolysis and cross-metathesis applied to plant oil derivatives will show new routes to fine chemicals, bifunctional products, polymer precursours and industry intermediates.

  11. Ligand-controlled C(sp³)-H arylation and olefination in synthesis of unnatural chiral α-amino acids.

    PubMed

    He, Jian; Li, Suhua; Deng, Youqian; Fu, Haiyan; Laforteza, Brian N; Spangler, Jillian E; Homs, Anna; Yu, Jin-Quan

    2014-03-14

    The use of ligands to tune the reactivity and selectivity of transition metal catalysts for C(sp(3))-H bond functionalization is a central challenge in synthetic organic chemistry. Herein, we report a rare example of catalyst-controlled C(sp(3))-H arylation using pyridine and quinoline derivatives: The former promotes exclusive monoarylation, whereas the latter activates the catalyst further to achieve diarylation. Successive application of these ligands enables the sequential diarylation of a methyl group in an alanine derivative with two different aryl iodides, affording a wide range of β-Ar-β-Ar'-α-amino acids with excellent levels of diastereoselectivity (diastereomeric ratio > 20:1). Both configurations of the β-chiral center can be accessed by choosing the order in which the aryl groups are installed. The use of a quinoline derivative as a ligand also enables C(sp(3))-H olefination of a protected alanine.

  12. Asymmetric cyclopropanation of olefins catalysed by Cu(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*).

    PubMed

    Castano, Brunilde; Guidone, Stefano; Gallo, Emma; Ragaini, Fabio; Casati, Nicola; Macchi, Piero; Sisti, Massimo; Caselli, Alessandro

    2013-02-21

    The synthesis and characterisation of copper(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*) and their use as catalysts in asymmetric cyclopropanation reactions are reported. All ligands and metal complexes were fully characterised, including crystal structures of some species determined by X-ray diffraction on single crystals. This allowed characterising the very different conformations of the macrocycles which could be induced by different substituents or by metal complexation. The strategy adopted for the ligand synthesis is very flexible allowing several structural modifications. A small library of macrocyclic ligands possessing the same donor properties but with either C(1) or C(2) symmetry was synthesized. Cyclopropane products with both aromatic and aliphatic olefins were obtained in good yields and enantiomeric excesses up to 99%.

  13. Chloride-Bridged Dinuclear Rhodium(III) Complexes Bearing Chiral Diphosphine Ligands: Catalyst Precursors for Asymmetric Hydrogenation of Simple Olefins.

    PubMed

    Kita, Yusuke; Hida, Shoji; Higashihara, Kenya; Jena, Himanshu Sekhar; Higashida, Kosuke; Mashima, Kazushi

    2016-07-11

    Efficient rhodium(III) catalysts were developed for asymmetric hydrogenation of simple olefins. A new series of chloride-bridged dinuclear rhodium(III) complexes 1 were synthesized from the rhodium(I) precursor [RhCl(cod)]2 , chiral diphosphine ligands, and hydrochloric acid. Complexes from the series acted as efficient catalysts for asymmetric hydrogenation of (E)-prop-1-ene-1,2-diyldibenzene and its derivatives without any directing groups, in sharp contrast to widely used rhodium(I) catalytic systems that require a directing group for high enantioselectivity. The catalytic system was applied to asymmetric hydrogenation of allylic alcohols, alkenylboranes, and unsaturated cyclic sulfones. Control experiments support the superiority of dinuclear rhodium(III) complexes 1 over typical rhodium(I) catalytic systems. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Divergent Strategy for the Diastereoselective Synthesis of the Tricyclic 6,7-Diaryltetrahydro-6H-benzo[c]chromene Core via Pt(IV)-Catalyzed Cycloaddition of o-Quinone Methides and Olefin Ring-Closing Metathesis.

    PubMed

    Tangdenpaisal, Kassrin; Chuayboonsong, Kanokpish; Ruchirawat, Somsak; Ploypradith, Poonsakdi

    2017-03-03

    A divergent strategy for the synthesis of the tricyclic 6,7-diaryltetrahydro-6H-benzo[c]chromene core was successfully developed. The 2,3-trans, 2,4-cis trisubstituted chroman moiety was formed via highly efficient and stereoselective Pt(IV)-catalyzed cycloaddition reactions of the corresponding quinone methides with chalcones. Subsequent steps provided the common diene alcohol, which underwent BF3·Et2O-mediated Et3SiH reduction and olefin ring-closing metathesis (RCM) using Ru(II) catalysts. The sequence of the final two steps provided a handle to diversify the stereochemical outcomes at C6 as well as C10a.

  15. Organometallic chemistry: A new metathesis

    NASA Astrophysics Data System (ADS)

    Hennessy, Elisabeth T.; Jacobsen, Eric N.

    2016-08-01

    Carbonyls and alkenes, two of the most common functional groups in organic chemistry, generally do not react with one another. Now, a simple Lewis acid has been shown to catalyse metathesis between alkenes and ketones in a new carbonyl olefination reaction.

  16. Separation of planar chiral ferrocene derivatives on beta-cyclodextrin-based polymer supports prepared via ring-opening metathesis graft-polymerization.

    PubMed

    Mayr, Betina; Schottenberger, Herwig; Elsnerb, Olaf; Buchmeiser, Michael R

    2002-10-11

    A series of beta-cyclodextrin (beta-CD) based chiral stationary phases (CSPs) were synthesized by ring-opening metathesis graft polymerization of various norborn-2-ene (NBE) substituted CDs. Chiral selectors based on endo/exo-6-O-(norborn-2-ene-5-ylmethoxymethylsilyl)-beta-CD, tris(endo/exo-6-O-norborn-2-ene-5-ylmethoxymethylsilyl)-beta-CD, tetrakis(endolexo-6-0-norborn-2-ene-5-ylmethoxymethylsilyl)-beta-CD, hexakis(endo/exo-6-O-norborn-2-ene-5-ylmethoxymethylsilyl)-beta-CD and tetrakis(endo-6-O-norborn-2-ene-5-carboxyl)-beta-CD were grafted onto Nucleosil 300-5 using well-established grafting procedures. CSPs were investigated for their separation capabilities for a series of the planar chiral ferrocene derivatives, rac-ferroceno[2,3a]inden-1-one (1a, 1b), rac-6-(3-hydroxy-3-methylbut-1-yn-1-yl)ferroceno[2,3a]inden-1-one (2a, 2b), rac-ferrocene[2,3a]indene (3a, 3b), rac-endo 1-methoxy-1-allylferroceno[2,3a]indene (4a, 4b) and rac-1,4-dihydroxybutylferrocene (5a, 5b). Compounds la, lb and 2a, 2b bearing a carbonyl group were successfully separated on these CSPs, while compounds 3-5 do not undergo enantioselective interaction under the conditions applied. General aspects of separation as well as mechanistic implementations are discussed.

  17. CH3-ReO3 on gamma-Al2O3: understanding its structure, initiation,and reactivity in olefin metathesis

    SciTech Connect

    Salameh, Alain; Joubert, Jerome; Baudouin, Anne; Lukens, Wayne; Delbecq, Francoise; Sautet, Philippe; Basset, Jean Marie; Coperet,Christophe

    2007-01-20

    Me-ReO3 on gamma-alumina: understanding the structure, theinitiation and thereactivity of a highly active olefin metathesiscatalyst Heterolytic splitting of the C-H bond of the methyl group ofCH3ReO3 on AlsO reactive sites of alumina as a way to generate the activesite of CH3ReO3 supported on gamma-Al203.

  18. Tandem Ring-Opening-Ring-Closing Metathesis for Functional Metathesis Catalysts.

    PubMed

    Nagarkar, Amit A; Yasir, Mohammad; Crochet, Aurelien; Fromm, Katharina M; Kilbinger, Andreas F M

    2016-09-26

    Use of a tandem ring-opening-ring-closing metathesis (RORCM) strategy for the synthesis of functional metathesis catalysts is reported. Ring opening of 7-substituted norbornenes and subsequent ring-closing metathesis forming a thermodynamically stable 6-membered ring lead to a very efficient synthesis of new catalysts from commercially available Grubbs' catalysts. Hydroxy functionalized Grubbs' first- as well as third-generation catalysts have been synthesized. Mechanistic studies have been performed to elucidate the order of attack of the olefinic bonds. This strategy was also used to synthesize the ruthenium methylidene complex. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. On the enantioselective olefin epoxidation by doubly bridged biphenyl azepine derivatives--mixed tropos/atropos chiral biaryls.

    PubMed

    Vachon, Jérôme; Rentsch, Samuel; Martinez, Alexandre; Marsol, Claire; Lacour, Jérôme

    2007-02-07

    Diastereomeric doubly bridged biphenyl azepines, atropos at 20 degrees C and tropos at 80 degrees C, are precursors to effective iminium organocatalysts that are employed in the enantioselective epoxidation of prochiral olefins (up to 85% ee).

  20. Nickel-catalyzed enantioselective alkylative coupling of alkynes and aldehydes: synthesis of chiral allylic alcohols with tetrasubstituted olefins.

    PubMed

    Yang, Yun; Zhu, Shou-Fei; Zhou, Chang-Yue; Zhou, Qi-Lin

    2008-10-29

    A highly efficient nickel-catalyzed asymmetric alkylative coupling of alkynes, aldehydes, and dimethylzinc has been realized by using bulky spirobiindane phosphoramidite ligands, affording allylic alcohols with a tetrasubstituted olefin functionality in high yields, high regioselectivities, and excellent enantioselectivities.

  1. Axially coordinated chiral salen Mn(III) anchored onto azole onium modified ZnPS-PVPA as effective catalysts for asymmetric epoxidation of unfunctionalized olefins.

    PubMed

    Huang, Jing; Fu, Xiangkai; Wang, Gang; Miao, Qiang; Wang, Guomin

    2012-09-21

    A series of chiral salen Mn(III) immobilized onto azole onium modified zinc poly(styrene-phenylvinyl phosphonate)-phosphate (ZnPS-PVPA) were prepared. The catalysts were characterized by FT-IR, diffusion reflection UV-vis, AAS, N(2) volumetric adsorption, SEM, TEM, XPS, XRD, TG and elemental analysis. The results showed that the chiral salen Mn(III) complex was successfully immobilized onto ZnPS-PVPA. These prepared catalysts were evaluated in the asymmetric epoxidation of unfunctionalized olefins with m-CPBA and NaIO(4) as oxidants and demonstrated higher catalytic activities than those of the corresponding homogeneous chiral salen Mn(III) catalyst under the same conditions. Moreover, these heterogeneous catalysts were stable and could be recycled nine times without significant loss of activity. Furthermore, this novel type of catalyst could also be validly used in large-scale reactions with superior catalytic disposition being maintained at the same level, which indicated the potential for applications in industry.

  2. Metathesis of alkanes and related reactions.

    PubMed

    Basset, Jean-Marie; Copéret, Christophe; Soulivong, Daravong; Taoufik, Mostafa; Cazat, Jean Thivolle

    2010-02-16

    The transformation of alkanes remains a difficult challenge because of the relative inertness of the C-H and C-C bonds. The rewards for asserting synthetic control over unfunctionalized, saturated hydrocarbons are considerable, however, because converting short alkanes into longer chain analogues is usually a value-adding process. Alkane metathesis is a novel catalytic and direct transformation of two molecules of a given alkane into its lower and higher homologues; moreover, the process proceeds at relatively low temperature (ambient conditions or higher). It was discovered through the use of a silica-supported tantalum hydride, ([triple bond]SiO)(2)TaH, a multifunctional catalyst with a single site of action. This reaction completes the story of the metathesis reactions discovered over the past 40 years: olefin metathesis, alkyne metathesis, and ene-yne cyclizations. In this Account, we examine the fundamental mechanistic aspects of alkane metathesis as well as the novel reactions that have been derived from its study. The silica-supported tantalum hydride catalyst was developed as the result of systematic and meticulous studies of the interaction between oxide supports and organometallic complexes, a field of study denoted surface organometallic chemistry (SOMC). A careful examination of this surface-supported tantalum hydride led to the later discovery of alumina-supported tungsten hydride, W(H)(3)/Al(2)O(3), which proved to be an even better catalyst for alkane metathesis. Supported tantalum and tungsten hydrides are highly unsaturated, electron-deficient species that are very reactive toward the C-H and C-C bonds of alkanes. They show a great versatility in various other reactions, such as cross-metathesis between methane and alkanes, cross-metathesis between toluene and ethane, or even methane nonoxidative coupling. Moreover, tungsten hydride exhibits a specific ability in the transformation of isobutane into 2,3-dimethylbutane as well as in the metathesis

  3. Nonproductive events in ring-closing metathesis using ruthenium catalysts.

    PubMed

    Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

    2010-06-30

    The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

  4. Ru-Based Z-Selective Metathesis Catalysts with Modified Cyclometalated Carbene Ligands†

    PubMed Central

    Bronner, Sarah M.; Herbert, Myles B.; Patel, Paresma R.; Marx, Vanessa M.; Grubbs, Robert H.

    2014-01-01

    A series of cyclometalated Z-selective ruthenium olefin metathesis catalysts with alterations to the N-heterocyclic carbene (NHC) ligand were prepared. X-Ray crystal structures of several new catalysts were obtained, elucidating the structural features of this class of cyclometalated complexes. The metathesis activity of each stable complex was evaluated, and one catalyst, bearing geminal dimethyl backbone substitution, was found to be comparable to our best Z-selective metathesis catalyst to date. PMID:25346842

  5. Building Indenylidene-Ruthenium Catalysts for Metathesis Transformations

    NASA Astrophysics Data System (ADS)

    Clavier, Hervé; Nolan, Steven P.

    Ruthenium-mediated olefin metathesis has emerged as an indispensable tool in organic synthesis for the formation carbon-carbon double bonds, attested by the large number of applications for natural product synthesis. Among the numerous catalysts developed to mediate olefin metathesis transformations, ruthenium-indenylidene complexes are robust and powerful pre-catalysts. The discovery of this catalyst category was slightly muddled due to a first mis-assignment of the compound structure. This report provides an overview of the synthetic routes for the construction of the indenylidene pattern in ruthenium complexes. The parameters relating to the indenylidene moiety construction will be discussed as well as the mechanism of this formation

  6. Lewis basicity modulation of N-heterocycles: a key for successful cross-metathesis.

    PubMed

    Lafaye, Kevin; Nicolas, Lionel; Guérinot, Amandine; Reymond, Sébastien; Cossy, Janine

    2014-10-03

    Cross-metathesis involving N-heteroaromatic olefinic derivatives is disclosed. The introduction of an appropriate substituent on the heteroaromatic ring decreases the Lewis basicity of the nitrogen atom, thus preventing the deactivation of the ruthenium-centered catalyst. The reaction is quite general in terms of both N-heterocycles and olefinic partners.

  7. Induction of Olefin Metathesis by Acetylenes.

    DTIC Science & Technology

    1980-11-20

    essentially that of 2. The acetylene is thus an activator, but unlike the organometallic co- catalysts like C2 H5A1C1 2 , which it replaces, it is unique in...J.C.; Moulijn, J.A. Adv. Catal. 1975, 24, 131. (4) Some of the results were discussed at the 3rd NSF Workshop on Organo - metallic Chemistry, Pingree

  8. Rh-catalyzed asymmetric hydrogenation of prochiral olefins with a dynamic library of chiral TROPOS phosphorus ligands.

    PubMed

    Monti, Chiara; Gennari, Cesare; Piarulli, Umberto; de Vries, Johannes G; de Vries, André H M; Lefort, Laurent

    2005-11-04

    A library of 19 chiral tropos phosphorus ligands, based on a flexible (tropos) biphenol unit and a chiral P-bound alcohol (11 phosphites) or secondary amine (8 phosphoramidites), was synthesized. These ligands were screened, individually and as a combination of two, in the rhodium-catalyzed asymmetric hydrogenation of dehydro-alpha-amino acids, dehydro-beta-amino acids, enamides and dimethyl itaconate. ee values up to 98% were obtained for the dehydro-alpha-amino acids, by using the best combination of ligands, a phosphite [4-P(O)2O] and a phosphoramidite [13-P(O)2N]. Kinetic studies of the reactions with the single ligands and with the combination of phosphite [4-P(O)2O] and phosphoramidite [13-P(O)2N] have shown that the phosphite, despite being less enantioselective, promotes the hydrogenation of methyl 2-acetamidoacrylate and methyl 2-acetamidocinnamate faster than the mixture of the same phosphite with the phosphoramidite, while the phosphoramidite alone is much less active. In this way, the reaction was optimized by lowering the phosphite/phosphoramidite ratio (the best ratio is 0.25 equiv phosphite/1.75 equiv phosphoramidite) with a resulting improvement of the product enantiomeric excess. A simple mathematical model for a better understanding of the variation of the enantiomeric excess with the phosphite/phosphoramidite ratio is also presented.

  9. Dinuclear manganese complexes containing chiral 1,4,7-triazacyclononane-derived ligands and their catalytic potential for the oxidation of olefins, alkanes, and alcohols.

    PubMed

    Romakh, Vladimir B; Therrien, Bruno; Süss-Fink, Georg; Shul'pin, Georgiy B

    2007-02-19

    Five new 1,4,7-triazacyclononane-derived compounds, sodium 3-(4,7-dimethyl-1,4,7-triazacyclononan-1-yl)propionate (Na[LMe2R']) as well as the enantiopure derivatives (S)-1-(2-methylbutyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R''), SS-trans-2,5,8-trimethyl-2,5,8-triazabicyclo[7.4.01,9]tridecane (SS-LBMe3), (S)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (S-LMe2R), and (R)-1-(2-hydroxypropyl)-4,7-dimethyl-1,4,7-triazacyclononane (R-LMe2R), have been synthesized. Reaction of manganese dichloride with the chiral macrocycles S-LMe2R and R-LMe2R in aqueous ethanol gives, upon oxidation with hydrogen peroxide, the brown dinuclear Mn(III)-Mn(IV) complexes which are enantiomers, [Mn2(S-LMe2R)2(mu-O)2]3+ (S,S-1) and [Mn2(R-LMe2R)2(mu-O)2]3+ (R,R-1). The single-crystal X-ray structure analyses of [S,S-1][PF6]3.0.5(CH3)2CO and [R,R-1][PF6]3.0.5(CH3)2CO show both enantiomers to contain Mn(III) and Mn(IV) centers, each of which being coordinated to three nitrogen atoms of a triazacyclononane ligand and each of which being bridged by two oxo and by two chiral hydroxypropyl pendent arms of the macrocycle. The enantiomeric complexes S,S-1 and R,R-1 were found to catalyze the oxidation of olefins, alkanes, and alcohols with hydrogen peroxide. In the epoxidation of indene the enantiomeric excess values attain 13%. The bond selectivities of the oxidation of linear and branched alkanes suggest the crucial step in this process to be the attack of a sterically hindered high-valent manganese-oxo species on the C-H bond.

  10. Methods of making organic compounds by metathesis

    DOEpatents

    Abraham, Timothy W.; Kaido, Hiroki; Lee, Choon Woo; Pederson, Richard L.; Schrodi, Yann; Tupy, Michael John

    2015-09-01

    Described are methods of making organic compounds by metathesis chemistry. The methods of the invention are particularly useful for making industrially-important organic compounds beginning with starting compositions derived from renewable feedstocks, such as natural oils. The methods make use of a cross-metathesis step with an olefin compound to produce functionalized alkene intermediates having a pre-determined double bond position. Once isolated, the functionalized alkene intermediate can be self-metathesized or cross-metathesized (e.g., with a second functionalized alkene) to produce the desired organic compound or a precursor thereto. The method may be used to make bifunctional organic compounds, such as diacids, diesters, dicarboxylate salts, acid/esters, acid/amines, acid/alcohols, acid/aldehydes, acid/ketones, acid/halides, acid/nitriles, ester/amines, ester/alcohols, ester/aldehydes, ester/ketones, ester/halides, ester/nitriles, and the like.

  11. Decomposition Pathways of Z-Selective Ruthenium Metathesis Catalysts

    PubMed Central

    Herbert, Myles B.; Lan, Yu; Keitz, Benjamin K.; Liu, Peng; Endo, Koji; Day, Michael W.; Houk, K. N.; Grubbs, Robert H.

    2012-01-01

    The decomposition of a Z-selective ruthenium metathesis catalyst and structurally similar analogs has been investigated utilizing X-ray crystallography and density functional theory. Isolated X-ray crystal structures suggest that recently reported C-H activated catalysts undergo decomposition via insertion of the alkylidene moiety into the chelating ruthenium-carbon bond followed by hydride elimination, which is supported by theoretical calculations. The resulting ruthenium hydride intermediates have been implicated in previously observed olefin migration, and thus lead to unwanted byproducts in cross metathesis reactions. Preventing these decomposition modes will be essential in the design of more active and selective Z-selective catalysts. PMID:22500642

  12. Controlled Ring-Opening Metathesis Polymerization by Molybdenum and Tungsten Alkylidene Complexes

    DTIC Science & Technology

    1988-07-29

    weights and low polydispersities (as low as 1.03) consistent with a living catalyst system employing 50, 100, 200, and 400 eq of monomer. The reactions are...secondary metathesis of polymer chains Bulky alkoxide ligands Wittig-like reaction Ring-opening metathesis polymerization (ROMP) Feast monomer Cyclic...olefins Retro Diels-Alder reaction Norbornene (NBE) Low temperature column chromatography Endo-,endo-5,6-dicarbomethoxynorbornene Discrete, soluble

  13. Concise Syntheses of Insect Pheromones Using Z-Selective Cross Metathesis**

    PubMed Central

    Herbert, Myles B.; Marx, Vanessa M.; Pederson, Richard L.; Grubbs, Robert H.

    2013-01-01

    The shortest synthetic routes to nine cis-pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z-olefins. Important insight into the mechanism of Z-selective metathesis was uncovered during experimentation and subsequently explored. PMID:23055437

  14. Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

    PubMed Central

    Balof, Shawna L; Nix, K Owen; Olliff, Matthew S; Roessler, Sarah E; Saha, Arpita; Müller, Kevin B; Behrens, Ulrich; Valente, Edward J

    2015-01-01

    Summary Three new ruthenium alkylidene complexes (PCy3)Cl2(H2ITap)Ru=CHSPh (9), (DMAP)2Cl2(H2ITap)Ru=CHPh (11) and (DMAP)2Cl2(H2ITap)Ru=CHSPh (12) have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl)-4,5-dihydroimidazol-2-ylidene). Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP) and ring closing metathesis (RCM) reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA), however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD) and mixtures of DCPD with cyclooctene (COE) in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes. PMID:26664616

  15. Olefin hydration

    SciTech Connect

    Butt, M.H.D.; Waller, F.J.

    1993-08-03

    An improved process for the hydration of olefins to alcohols is described wherein the improvement comprises contacting said olefins with the catalytic composition comprising a perfluorinated ion-exchange polymer containing sulfonic acid groups supported on an inert carrier wherein said carrier comprises calcined shot coke with a mean pore diameter of about 1,000 Angstroms in the presence of water at a temperature of from about 180 C to about 250 C.

  16. Concise syntheses of insect pheromones using Z-selective cross metathesis.

    PubMed

    Herbert, Myles B; Marx, Vanessa M; Pederson, Richard L; Grubbs, Robert H

    2013-01-02

    Very short synthetic routes to nine cis-olefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported. These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Unconventional olefin processes

    SciTech Connect

    Hu, Y.C.

    1983-05-01

    The conversion of syngas into olefins is based on the Fischer-Tropsch technology. The FT modified process for olefins includes: upgraded liquids for olefins and aromatics, and catcracking of methanol. Because of the number of catalysts for olefins, data is not yet possible. Economic projections suggest that methanol cracking for olefins will be feasible in 1990. Olefin demand will grow, and C/sub 1/ chemistry research will increase, so that some unconventional olefin processes can be commercialized by then.

  18. Preparation of cadmium selenide-polyolefin composites from functional phosphine oxides and ruthenium-based metathesis.

    PubMed

    Skaff, Habib; Ilker, M Firat; Coughlin, E Bryan; Emrick, Todd

    2002-05-22

    Cadmium selenide nanoparticles, prepared by known methods, were stabilized with functional phosphine oxide 1, then used to support the polymerization of cyclic olefins radially outward from the surface by ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The conversion of compound 1 into the new metathesis catalyst 3 by carbene exchange and the subsequent polymerization of cyclic olefins were observed spectroscopically by (1)H NMR to afford for example CdSe-polycyclooctene composite 6. Transmission electron micrographs on thin films of these composites showed good nanoparticle dispersion. This is in stark contrast to the substantial nanoparticle aggregation observed when similar polymerizations were performed in the presence of conventional TOPO-covered nanoparticles. The methods reported here to prepare composite product 6 are applicable to other cyclic olefins, and suggest that this chemistry will be useful for incorporating CdSe nanoparticles into a wide variety of polymer matrices.

  19. Tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds.

    PubMed

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando; Del Pozo, Carlos; Fustero, Santos

    2015-01-01

    A new tandem cross enyne metathesis (CEYM)-intramolecular Diels-Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM-IMDAR protocols.

  20. Absence of the Thorpe–Ingold Effect by gem-Diphenyl Groups in Ring-Closing Enyne Metathesis

    PubMed Central

    Kim, Yi Jin; Grimm, Jonathan B.; Lee, Daesung

    2007-01-01

    In tandem ring-closing metathesis of alkynyl silaketals containing two different tethered olefins, the gem-dimethyl group showed the expected Thorpe-Ingold effect, thereby giving good level of group selectivity. Unexpectedly, however, the corresponding gem-diphenyl group did not show any Thorpe-Ingold effect for the ring closure reaction. PMID:18046462

  1. Cross metathesis for the synthesis of novel C-sialosides.

    PubMed

    Meinke, Sebastian; Thiem, Joachim

    2008-07-21

    Cross metathesis of both anomers of C-allyl sialoside (3alpha/3beta) with styrene catalyzed by the second generation Grubbs or Hoveyda-Grubbs catalysts gave the corresponding aryl derivatives (4alpha/4beta) in virtually quantitative yields. The products were hydrogenated to model compounds 5alpha/5beta. Similarly, reaction of the alpha-anomer 3alpha with galactose derivative 8 gave the olefin-linked disaccharide mimetic 9. Following hydrogenation and deprotection, the ethylene-bridged Neu5Acalpha(2-->6)Gal analogue 11 could be obtained.

  2. Z-Selective Ethenolysis With a Ruthenium Metathesis Catalyst: Experiment and Theory

    PubMed Central

    Miyazaki, Hiroshi; Herbert, Myles B.; Liu, Peng; Dong, Xiaofei; Xu, Xiufang; Keitz, Benjamin K.; Ung, Thay; Mkrtumyan, Garik; Houk, K. N.; Grubbs, Robert H.

    2013-01-01

    The Z-selective ethenolysis activity of chelated ruthenium metathesis catalysts was investigated with experiment and theory. A five-membered chelated catalyst that was successfully employed in Z-selective cross metathesis reactions has now been found to be highly active for Z-selective ethenolysis at low ethylene pressures, while tolerating a wide variety of functional groups. This phenomenon also affects its activity in cross metathesis reactions and prohibits crossover reactions of internal olefins via trisubstituted ruthenacyclobutane intermediates. In contrast, a related catalyst containing a six-membered chelated architecture is not active for ethenolysis and seems to react through different pathways more reminiscent of previous generations of ruthenium catalysts. Computational investigations of the effects of substitution on relevant transition states and ruthenacyclobutane intermediates revealed that the differences of activities are attributed to the steric repulsions of the anionic ligand with the chelating groups. PMID:23547887

  3. Prosodically Driven Metathesis in Mutsun

    ERIC Educational Resources Information Center

    Butler, Lynnika

    2013-01-01

    Among the many ways in which sounds alternate in the world's languages, changes in the order of sounds (metathesis) are relatively rare. Mutsun, a Southern Costanoan language of California which was documented extensively before the death of its last speaker in 1930, displays three patterns of synchronic consonant-vowel (CV) metathesis. Two of…

  4. Prosodically Driven Metathesis in Mutsun

    ERIC Educational Resources Information Center

    Butler, Lynnika

    2013-01-01

    Among the many ways in which sounds alternate in the world's languages, changes in the order of sounds (metathesis) are relatively rare. Mutsun, a Southern Costanoan language of California which was documented extensively before the death of its last speaker in 1930, displays three patterns of synchronic consonant-vowel (CV) metathesis. Two of…

  5. Primary products and mechanistic considerations in alkane metathesis.

    PubMed

    Basset, Jean Marie; Copéret, Christophe; Lefort, Laurent; Maunders, Barry M; Maury, Olivier; Le Roux, Erwan; Saggio, Guillaume; Soignier, Sophie; Soulivong, Daravong; Sunley, Glenn J; Taoufik, Mostafa; Thivolle-Cazat, Jean

    2005-06-22

    Alkane metathesis, a reaction catalyzed by the silica-supported tantalum hydride [(SiO)2Ta-H], 1, which transforms acyclic alkanes into their higher and lower homologues, was reported in 1997. New studies conducted in a continuous flow reactor in the case of propane indicate that, by varying the contact time, hydrogen and olefins are primary products. This crucial observation, as well as the known properties of tantalum alkyls to perform alpha-H or beta-H eliminations, supports the proposition of a new mechanism involving metallacyclobutane intermediates just like in olefin metathesis. The observed selectivities for linear and branched Cn+1 and Cn+2 products as well as the linear/branched ratio can be well-explained on the basis of the minimization of steric interactions between 1,2- or 1,3-substituents in the various tantallacyclobutane intermediates or during their formation. Hydrogen plays a specific role in the cleavage of metal alkyls to complete the catalytic cycle.

  6. Enantioselective Rh-Catalyzed Hydroacylation of Olefins: From Serendipitous Discovery to Rational Design

    PubMed Central

    Murphy, Stephen K.

    2015-01-01

    Rh-catalysed hydroacylation allows the construction of chiral ketones from olefins and aldehydes. Since James' and Young's serendipitous discovery of the enantioselective 4-pentenal cyclisation, both intra and intermolecular variants have emerged that enable broader applications. PMID:25277153

  7. Electrochemical Os-mediated asymmetric dihydroxylation of olefins

    SciTech Connect

    Torii, Sigeru

    1995-12-31

    Recently, the effective chiral ligands for enantioselective dihydroxylation of olefins have intensively been investigated. Among the reported asymmetric dihydroxylation systems, the superiority of a H{sub 2}O/t-BuOH-K{sub 3}Fe(CN){sub 6}/K{sub 2}CO{sub 3} system with chiral ligands, i.e., DHQD and/or DHQ derivatives, has been mentioned. Herein, the authors disclose preliminary studies on the electrochemical Os-catalyzed asymmetric dihyroxylation of olefins with Sharpless` ligands (L*).

  8. Olefin Metathesis in Peptidomimetics, Dynamic Combinatorial Chemistry, and Molecular Imprinting

    DTIC Science & Technology

    2006-08-01

    inhibitor against an enzyme found in bacteria .26 Scheme 2-3. Retrosynthethic analysis of 2-6...potential HIV protease inhibitors by grafting pharmacophoric groups on a azasugar scaffold (Figure 1-4),46 but a rather lengthy synthetic scheme starting...macrocyclic lactams is shown in Scheme 2- 2, in which Pei et al. discovered that 15-17 membered rings provided the best inhibitor properties against an

  9. Catalytic enantioselective synthesis of naturally occurring butenolides via hetero-allylic alkylation and ring closing metathesis.

    PubMed

    Mao, Bin; Geurts, Koen; Fañanás-Mastral, Martín; van Zijl, Anthoni W; Fletcher, Stephen P; Minnaard, Adriaan J; Feringa, Ben L

    2011-03-04

    An efficient catalytic asymmetric synthesis of chiral γ-butenolides was developed based on the hetero-allylic asymmetric alkylation (h-AAA) in combination with ring closing metathesis (RCM). The synthetic potential of the h-AAA-RCM protocol was illustrated with the facile synthesis of (-)-whiskey lactone, (-)-cognac lactone, (-)-nephrosteranic acid, and (-)-roccellaric acid.

  10. Highly efficient molybdenum-based catalysts for enantioselective alkene metathesis

    PubMed Central

    Malcolmson, Steven J.; Meek, Simon J.; Sattely, Elizabeth S.; Schrock, Richard R.; Hoveyda, Amir H.

    2009-01-01

    Discovery of efficient catalysts is one of the most compelling objectives of modern chemistry. Chiral catalysts are in particularly high demand, as they facilitate synthesis of enantiomerically enriched small molecules that are critical to developments in medicine, biology and materials science1. Especially noteworthy are catalysts that promote—with otherwise inaccessible efficiency and selectivity levels—reactions demonstrated to be of great utility in chemical synthesis. Here we report a class of chiral catalysts that initiate alkene metathesis1 with very high efficiency and enantioselectivity. Such attributes arise from structural fluxionality of the chiral catalysts and the central role that enhanced electronic factors have in the catalytic cycle. The new catalysts have a stereogenic metal centre and carry only monodentate ligands; the molybdenum-based complexes are prepared stereoselectively by a ligand exchange process involving an enantiomerically pure aryloxide, a class of ligands scarcely used in enantioselective catalysis2,3. We demonstrate the application of the new catalysts in an enantioselective synthesis of the Aspidosperma alkaloid, quebrachamine, through an alkene metathesis reaction that cannot be promoted by any of the previously reported chiral catalysts. PMID:19011612

  11. Expanding the scope of metathesis: a survey of polyfunctional, single-site supported tungsten systems for hydrocarbon valorization.

    PubMed

    Popoff, Nicolas; Mazoyer, Etienne; Pelletier, Jérémie; Gauvin, Régis M; Taoufik, Mostafa

    2013-12-07

    Olefin metathesis is increasingly incorporated in polyfunctional industrial processes. The classical WO3/SiO2 olefin metathesis catalyst is combined to other catalysts in order to afford higher added-value chemicals. However, the combination of several reactions, not only in a single reactor, but also stemming from a single, multifunctional surface species is a desirable improvement regarding process issues. Well-defined surface organometallic tungsten species can be designed to implement targeted functionalities (carbene, hydride, alkyl, …). By tuning the metal's coordination sphere, it is possible to combine metathesis with several reactions, such as (de)hydrogenation, dimerization or isomerization. Novel, unconventional reactions for the production and upgrading of alkanes and alkenes have thus been uncovered. The reactivity of this library of supported catalysts is discussed based on the type of mediated transformations: monofunctional (alkene and alkyne metathesis), bifunctional (1-butene or 2-butenes to propylene), trifunctional (ethylene to propylene, alkane metathesis, …). Mechanistic considerations will be discussed to put these results in a wider perspective for future developments.

  12. Metathesis depolymerizable surfactants

    DOEpatents

    Jamison, Gregory M.; Wheeler, David R.; Loy, Douglas A.; Simmons, Blake A.; Long, Timothy M.; McElhanon, James R.; Rahimian, Kamyar; Staiger, Chad L.

    2008-04-15

    A class of surfactant molecules whose structure includes regularly spaced unsaturation in the tail group and thus, can be readily decomposed by ring-closing metathesis, and particularly by the action of a transition metal catalyst, to form small molecule products. These small molecules are designed to have increased volatility and/or enhanced solubility as compared to the original surfactant molecule and are thus easily removed by solvent extraction or vacuum extraction at low temperature. By producing easily removable decomposition products, the surfactant molecules become particularly desirable as template structures for preparing meso- and microstructural materials with tailored properties.

  13. Metathesis catalysts and methods thereof

    DOEpatents

    Schrock, Richard Royce; Yuan, Jian

    2016-04-19

    The present application provides, among other things, novel compounds for metathesis reactions, and methods for preparing and using provided compounds. In some embodiments, the present invention provides compounds having the structure of formula I or II. In some embodiments, the present invention provides methods for preparing a compound of formula I or II. In some embodiments, the present invention provides methods for using a provided compound. In some embodiments, a provided compound is useful for stereoselective ring-opening metathesis polymerization. In some embodiments, a provided metathesis method provides cis and/or isotactic polymers.

  14. Catalytic living ring-opening metathesis polymerization

    NASA Astrophysics Data System (ADS)

    Nagarkar, Amit A.; Kilbinger, Andreas F. M.

    2015-09-01

    In living ring-opening metathesis polymerization (ROMP), a transition-metal-carbene complex polymerizes ring-strained olefins with very good control of the molecular weight of the resulting polymers. Because one molecule of the initiator is required for each polymer chain, however, this type of polymerization is expensive for widespread use. We have now designed a chain-transfer agent (CTA) capable of reducing the required amount of metal complex while still maintaining full control over the living polymerization process. This new method introduces a degenerative transfer process to ROMP. We demonstrate that substituted cyclohexene rings are good CTAs, and thereby preserve the ‘living’ character of the polymerization using catalytic quantities of the metal complex. The resulting polymers show characteristics of a living polymerization, namely narrow molecular-weight distribution, controlled molecular weights and block copolymer formation. This new technique provides access to well-defined polymers for industrial, biomedical and academic use at a fraction of the current costs and significantly reduced levels of residual ruthenium catalyst.

  15. Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

    PubMed Central

    Miró, Javier; Sánchez-Roselló, María; Sanz, Álvaro; Rabasa, Fernando

    2015-01-01

    Summary A new tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR) has been carried out. It involves conjugated ketones, esters or amides bearing a remote olefin and aromatic alkynes as the starting materials. The overall process enables the preparation of a small family of linear bicyclic scaffolds in a very simple manner with moderate to good levels of diastereoselectivity. This methodology constitutes one of the few examples that employ olefins differently than ethylene in tandem CEYM–IMDAR protocols. PMID:26425205

  16. Tandem Z-selective cross metathesis – dihydroxylation for the synthesis of anti-1,2-diols**

    PubMed Central

    Dornan, Peter K.; Wickens, Zachary K.

    2015-01-01

    A stereoselective synthesis of anti-1,2-diols has been developed using a multitasking Ru-catalyst in an assisted tandem catalysis protocol. A cyclometalated ruthenium complex catalyzes first a Z-selective cross metathesis of two terminal olefins followed by a stereospecific dihydroxylation. Both steps are catalyzed by Ru, as the Ru-complex is converted to a dihydroxylation catalyst upon addition of NaIO4. A variety of olefins are transformed into valuable highly functionalized and stereodefined molecules. Mechanistic experiments are performed to probe the nature of the oxidation step and catalyst inhibition pathways. These experiments point the way to more broadly applicable tandem catalytic transformations. PMID:25914354

  17. Homogeneous catalysts for stereoregular olefin polymerization

    DOEpatents

    Marks, T.J.; Eisen, M.S.; Giardello, M.A.

    1995-10-03

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C{sub 5}R{prime}{sub 4{minus}x}R*{sub x})A(C{sub 5}R{double_prime}{sub 4{minus}y}R{double_prime}{prime}{sub y})MQ{sub p}, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R{prime}, R{double_prime}, R{double_prime}{prime}, and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3{>=}p{>=}0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form ``cation-like`` species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other {alpha}-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.

  18. Homogeneous catalysts for stereoregular olefin polymerization

    DOEpatents

    Marks, T.J.; Eisen, M.S.; Giardello, M.A.

    1994-07-19

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C[sub 5]R[prime][sub 4[minus]x]R*[sub x])-A-(C[sub 5]R[double prime][sub 4[minus]y]R[prime][double prime][sub y])-M-Q[sub p], where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R[prime], R[double prime], R[prime][double prime], and R* represent substituted and unsubstituted alkyl groups having 1--30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3 [<=] p [<=] 0. Related complexes may be prepared by alkylation of the corresponding dichlorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form cation-like'' species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other [alpha]-olefin polymerization can be effected with very high efficiency and isospecificity. 1 fig.

  19. Homogeneous catalysts for stereoregular olefin polymerization

    DOEpatents

    Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

    1995-01-01

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R"'.sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R"', and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

  20. Homogeneous catalysts for stereoregular olefin polymerization

    DOEpatents

    Marks, Tobin J.; Eisen, Moris S.; Giardello, Michael A.

    1994-01-01

    The synthesis, and use as precatalysts of chiral organozirconium complexes for olefin polymerization are disclosed, having the structure (C.sub.5 R'.sub.4-x R*.sub.x) A (C.sub.5 R".sub.4-y R'".sub.y) M Q.sub.p, where x and y represent the number of unsubstituted locations on the cyclopentadienyl ring; R', R", R'", and R* represent substituted and unsubstituted alkyl groups having 1-30 carbon atoms and R* is a chiral ligand; A is a fragment containing a Group 13, 14, 15, or 16 element of the Periodic Table; M is a Group 3, 4, or 5 metal of the Periodic Table; and Q is a hydrocarbyl radical, or halogen radical, with 3.ltoreq.p.ltoreq.o. Related complexes may be prepared by alkylation of the corresponding dichorides. In the presence of methylalumoxane or triarylborane cocatalysts, these complexes form "cation-like" species which are highly active for olefin polymerization. In combination with a Lewis acid cocatalyst, propylene or other .alpha.-olefin polymerization can be effected with very high efficiency and isospecificity.

  1. Alkene metathesis: the search for better catalysts.

    PubMed

    Deshmukh, Prashant H; Blechert, Siegfried

    2007-06-28

    Alkene metathesis catalyst development has made significant progress over recent years. Research in metathesis catalyst design has endeavoured to tackle three key issues: those of (i) catalyst efficiency and activity, (ii) substrate scope and selectivity--particularly stereoselective metathesis reactions--and (iii) the minimization of metal impurities and catalyst recycling. This article describes a brief history of metathesis catalyst development, followed by a survey of more recent research, with a particular emphasis on ruthenium catalysts.

  2. Biphasic enantioselective olefin epoxidation using Tropos dibenzoazepinium catalysts.

    PubMed

    Vachon, Jérôme; Pérollier, Céline; Monchaud, David; Marsol, Claire; Ditrich, Klaus; Lacour, Jérôme

    2005-07-22

    Several novel chiral iminium TRISPHAT [tris(tetrachlorobenzenediolato)phosphate(V)] salts combining a diphenylazepinium core, chiral exocyclic appendages, and lipophilic counterions have been prepared and tested in biphasic enantioselective olefin epoxidation conditions. Interestingly, the iminium salts derived from commercially available (S)- or (R)-1,2,2-trimethylpropylamine can display efficiency similar to those made from L-acetonamine. Variable-temperature NMR spectroscopy (VT-NMR) and circular dichroism (CD) experiments were performed in search of a correlation between good enantioselectivity in the products and high diastereomeric control of the biphenyl axial chirality of the catalysts.

  3. Relay cross metathesis reactions of vinylphosphonates.

    PubMed

    Malla, Raj K; Ridenour, Jeremy N; Spilling, Christopher D

    2014-01-01

    Dimethyl (β-substituted) vinylphosphonates do not readily undergo cross metathesis reactions with Grubbs catalyst and terminal alkenes. However, the corresponding mono- or diallyl vinylphosphonate esters undergo facile cross metathesis reactions. The improved reactivity is attributed to a relay step in the cross metathesis reaction mechanism.

  4. Synthesis of Catenane Structures via Ring-Closing Metathesis.

    PubMed

    Weck, Marcus; Mohr, Bernhard; Sauvage, Jean-Pierre; Grubbs, Robert H.

    1999-07-23

    This study presents a detailed description of a synthetic strategy to obtain catenane architectures through ring-closing metathesis. The approach is based on phenanthroline-based ligands containing terminal olefinic units that were designed to coordinate in a tetrahedral arrangement around a copper atom. Treatment of the assembled copper complexes with ruthenium catalyst 1 resulted in [2]catenates in high yields of 88-92%. Demetalation produced the corresponding [2]catenand in nearly quantitative yields. Hydrogenation of the catenates with Crabtree's catalyst and subsequent demetalation yielded fully saturated catenands. The presently described procedure makes [2]catenanes very accessible since the synthetic route consists of six steps (Schemes 2 and 4) from commercially available 1,10-phenanthroline, the overall yield being 51%.

  5. Terminating Platinum-Initiated Cation-Olefin Reactions with Simple Alkenes

    DTIC Science & Technology

    2011-05-05

    an asymmetric cascade cyclization was investigated using the chiral [P2PPt] 2+ com- plex (P2=DTBM-SEGPHOS, P=PMe3) 19. The combina- tion of a chiral ...P2 ligand and an achiral monodentate phosphine has been previously shown to catalyze cyclo- rearrangment reactions with high enantiomeric excess.[27...the chiral initiator efficiently and diastereoselectively activates a single olefin face. In summary, we report the results of a platinum(II

  6. Cascade Metathesis Reactions for the Synthesis of Taxane and Isotaxane Derivatives

    PubMed Central

    Ma, Cong; Letort, Aurélien; Aouzal, Rémi; Wilkes, Antonia; Maiti, Gourhari; Farrugia, Louis J.; Ricard, Louis

    2016-01-01

    Abstract Tricyclic isotaxane and taxane derivatives have been synthesized by a very efficient cascade ring‐closing dienyne metathesis (RCDEYM) reaction, which formed the A and B rings in one operation. When the alkyne is present at C13 (with no neighboring gem‐dimethyl group), the RCEDYM reaction leads to 14,15‐isotaxanes 16 a,b and 18 b with the gem‐dimethyl group on the A ring. If the alkyne is at the C11 position (and thus flanked by a gem‐dimethyl group), RCEDYM reaction only proceeds in the presence of a trisubstituted olefin at C13, which disfavors the competing diene ring‐closing metathesis reaction, to give the tricyclic core of Taxol 44. PMID:27062670

  7. Mechanistic Insights into Alkane Metathesis Catalyzed by Silica-Supported Tantalum Hydrides: A DFT Study.

    PubMed

    Núñez-Zarur, Francisco; Solans-Monfort, Xavier; Restrepo, Albeiro

    2017-09-05

    Alkane metathesis transforms small alkanes into their higher and lower homologues. The reaction is catalyzed by either supported d(0) metal hydrides (M = Ta, W) or d(0) alkyl alkylidene complexes (M = Ta, Mo, W, Re). For the silica-supported tantalum hydrides, several reaction mechanisms have been proposed. We performed DFT-D3 calculations to analyze the viability of the proposed pathways and compare them with alkane hydrogenolysis, which is a competitive process observed at the early stages of the reaction. The results show that the reaction mechanisms for alkane metathesis and for alkane hydrogenolysis present similar energetics, and this is consistent with the fact that the process taking place depends on the concentrations of the initial reactants. Overall, a modified version of the so-called one-site mechanism that involves alkyl alkylidene intermediates appears to be more likely and consistent with experiments. According to this proposal, tantalum hydrides are precursors of the alkyl alkylidene active species. During precursor activation, H2 is released and this allows alkane hydrogenolysis to occur. In contrast, the catalytic cycle implies only the reaction with alkane molecules in excess and does not form H2. Thus, the activity for alkane hydrogenolysis decreases. The catalytic cycle proposed here implies three stages: (i) β-H elimination from the alkyl ligand, liberating ethene, (ii) alkene cross-metathesis, allowing olefin substituent exchange, and (iii) formation of the final products and alkyl alkylidene regeneration by olefin insertion and three successive 1,2-CH insertions to the alkylidene followed by α abstraction. These results relate the reactivity of silica-supported hydrides with that of the alkyl alkylidene complexes, the other common catalyst for alkane metathesis.

  8. Room Temperature Ionic Liquids as Green Solvent Alternatives in the Metathesis of Oleochemical Feedstocks.

    PubMed

    Thomas, Priya A; Marvey, Bassy B

    2016-02-06

    One of the most important areas of green chemistry is the application of environmentally friendly solvents in catalysis and synthesis. Conventional organic solvents pose a threat to the environment due to the volatility, highly flammability, toxicity and carcinogenic properties they exhibit. The recently emerged room temperature ionic liquids (RTILs) are promising green solvent alternatives to the volatile organic solvents due to their ease of reuse, non-volatility, thermal stability and ability to dissolve a variety of organic and organometallic compounds. This review explores the use of RTILs as green solvent media in olefin metathesis for applications in the oleochemical industry.

  9. Kinetically E-selective macrocyclic ring-closing metathesis.

    PubMed

    Shen, Xiao; Nguyen, Thach T; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W H; Schrock, Richard R; Hoveyda, Amir H

    2017-01-19

    Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization-a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl-B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib-a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis-was prepared by RCM carried out at a substrate

  10. Kinetically E-selective macrocyclic ring-closing metathesis

    NASA Astrophysics Data System (ADS)

    Shen, Xiao; Nguyen, Thach T.; Koh, Ming Joo; Xu, Dongmin; Speed, Alexander W. H.; Schrock, Richard R.; Hoveyda, Amir H.

    2017-01-01

    Macrocyclic compounds are central to the development of new drugs, but preparing them can be challenging because of the energy barrier that must be surmounted in order to bring together and fuse the two ends of an acyclic precursor such as an alkene (also known as an olefin). To this end, the catalytic process known as ring-closing metathesis (RCM) has allowed access to countless biologically active macrocyclic organic molecules, even for large-scale production. Stereoselectivity is often critical in such cases: the potency of a macrocyclic compound can depend on the stereochemistry of its alkene; alternatively, one isomer of the compound can be subjected to stereoselective modification (such as dihydroxylation). Kinetically controlled Z-selective RCM reactions have been reported, but the only available metathesis approach for accessing macrocyclic E-olefins entails selective removal of the Z-component of a stereoisomeric mixture by ethenolysis, sacrificing substantial quantities of material if E/Z ratios are near unity. Use of ethylene can also cause adventitious olefin isomerization—a particularly serious problem when the E-alkene is energetically less favoured. Here, we show that dienes containing an E-alkenyl–B(pinacolato) group, widely used in catalytic cross-coupling, possess the requisite electronic and steric attributes to allow them to be converted stereoselectively to E-macrocyclic alkenes. The reaction is promoted by a molybdenum monoaryloxide pyrrolide complex and affords products at a yield of up to 73 per cent and an E/Z ratio greater than 98/2. We highlight the utility of the approach by preparing recifeiolide (a 12-membered-ring antibiotic) and pacritinib (an 18-membered-ring enzyme inhibitor), the Z-isomer of which is less potent than the E-isomer. Notably, the 18-membered-ring moiety of pacritinib—a potent anti-cancer agent that is in advanced clinical trials for treating lymphoma and myelofibrosis—was prepared by RCM carried out at a

  11. Recovery of olefin monomers

    SciTech Connect

    Golden, Timothy Christoph; Weist, Jr., Edward Landis; Johnson, Charles Henry

    2004-03-16

    In a process for the production of a polyolefin, an olefin monomer is polymerised said polyolefin and residual monomer is recovered. A gas stream comprising the monomer and nitrogen is subjected to a PSA process in which said monomer is adsorbed on a periodically regenerated silica gel or alumina adsorbent to recover a purified gas stream containing said olefin and a nitrogen rich stream containing no less than 99% nitrogen and containing no less than 50% of the nitrogen content of the gas feed to the PSA process.

  12. Living olefin polymerization processes

    DOEpatents

    Schrock, R.R.; Baumann, R.

    1999-03-30

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  13. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    1999-01-01

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  14. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Baumann, Robert

    2003-08-26

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  15. Living olefin polymerization processes

    DOEpatents

    Schrock, Richard R.; Bauman, Robert

    2006-11-14

    Processes for the living polymerization of olefin monomers with terminal carbon-carbon double bonds are disclosed. The processes employ initiators that include a metal atom and a ligand having two group 15 atoms and a group 16 atom or three group 15 atoms. The ligand is bonded to the metal atom through two anionic or covalent bonds and a dative bond. The initiators are particularly stable under reaction conditions in the absence of olefin monomer. The processes provide polymers having low polydispersities, especially block copolymers having low polydispersities. It is an additional advantage of these processes that, during block copolymer synthesis, a relatively small amount of homopolymer is formed.

  16. Selective olefin recovery

    SciTech Connect

    1996-07-01

    This report presents the results of the outstanding studies on olefin product purities, pyridine recovery, and absorber offgas utilization. Other reports issued since the May 2 technical review meeting in Grangemouth evaluated the impact of the new VLE data on the solution stripping operation and the olefin loadings in the lean and rich solutions. This report completes the bulk of Stone & Webster`s engineering development of the absorber/stripper process for Phase I. The final feasibility study report (to be issued in August) will present an updated design and economics.

  17. Retrofitting olefin cracking plants

    SciTech Connect

    Sumner, C.; Fernandez-Baujin, J.M.

    1983-12-01

    This article discusses the retrofitting of liquid crackers which produce olefins so that gaseous feedstocks can be used. Naphtha and gas oil are the predominant design feedstocks for producing olefins. The price of gaseous feedstocks such as ethane, propane and butane have become economically more attractive than liquid feedstocks. Existing liquid crackers will be able to produce ethylene at 85% or higher capacity when cracking propane and butane feedstock with only minor changes. Topics considered include revamping for vacuum gas oil (VGO) feedstocks and revamping for liquefied petroleum gas (LPG) feedstocks.

  18. Catalytic σ-Bond Metathesis

    NASA Astrophysics Data System (ADS)

    Reznichenko, Alexander L.; Hultzsch, Kai C.

    This account summarizes information on recently reported applications of organo-rare-earth metal complexes in various catalytic transformations of small molecules. The σ-bond metathesis at d0rare-earth metal centers plays a pivotal role in carbon-carbon and carbon-heteroatom bond forming processes. Relevant mechanistic details are discussed and the focus of the review lies in practical applications of organo-rare-earth metal complexes.

  19. Ring-Closing and Cross-Metathesis with Artificial Metalloenzymes Created by Covalent Active Site-Directed Hybridization of a Lipase.

    PubMed

    Basauri-Molina, Manuel; Verhoeven, Dide G A; van Schaik, Arnoldus J; Kleijn, Henk; Klein Gebbink, Robertus J M

    2015-10-26

    A series of Grubbs-type catalysts that contain lipase-inhibiting phosphoester functionalities have been synthesized and reacted with the lipase cutinase, which leads to artificial metalloenzymes for olefin metathesis. The resulting hybrids comprise the organometallic fragment that is covalently bound to the active amino acid residue of the enzyme host in an orthogonal orientation. Differences in reactivity as well as accessibility of the active site by the functionalized inhibitor became evident through variation of the anchoring motif and substituents on the N-heterocyclic carbene ligand. Such observations led to the design of a hybrid that is active in the ring-closing metathesis and the cross-metathesis of N,N-diallyl-p-toluenesulfonamide and allylbenzene, respectively, the latter being the first example of its kind in the field of artificial metalloenzymes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    PubMed Central

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-01-01

    Olefin metathesis has made a significant impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is very limited. In this manuscript, we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of an in situ-generated catalyst with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents and proceed to high conversion at ambient temperature within four hours. Many alkenyl chlorides, bromides and fluorides can be obtained in up to 91 percent yield and complete Z selectivity. This method can be used to easily synthesize biologically active compounds and to perform the site- and stereoselective fluorination of other organic compounds. PMID:27008965

  1. Direct synthesis of Z-alkenyl halides through catalytic cross-metathesis

    NASA Astrophysics Data System (ADS)

    Koh, Ming Joo; Nguyen, Thach T.; Zhang, Hanmo; Schrock, Richard R.; Hoveyda, Amir H.

    2016-03-01

    Olefin metathesis has had a large impact on modern organic chemistry, but important shortcomings remain: for example, the lack of efficient processes that can be used to generate acyclic alkenyl halides. Halo-substituted ruthenium carbene complexes decompose rapidly or deliver low activity and/or minimal stereoselectivity, and our understanding of the corresponding high-oxidation-state systems is limited. Here we show that previously unknown halo-substituted molybdenum alkylidene species are exceptionally reactive and are able to participate in high-yielding olefin metathesis reactions that afford acyclic 1,2-disubstituted Z-alkenyl halides. Transformations are promoted by small amounts of a catalyst that is generated in situ and used with unpurified, commercially available and easy-to-handle liquid 1,2-dihaloethene reagents, and proceed to high conversion at ambient temperature within four hours. We obtain many alkenyl chlorides, bromides and fluorides in up to 91 per cent yield and complete Z selectivity. This method can be used to synthesize biologically active compounds readily and to perform site- and stereoselective fluorination of complex organic molecules.

  2. Directed evolution of artificial metalloenzymes for in vivo metathesis

    NASA Astrophysics Data System (ADS)

    Jeschek, Markus; Reuter, Raphael; Heinisch, Tillmann; Trindler, Christian; Klehr, Juliane; Panke, Sven; Ward, Thomas R.

    2016-09-01

    The field of biocatalysis has advanced from harnessing natural enzymes to using directed evolution to obtain new biocatalysts with tailor-made functions. Several tools have recently been developed to expand the natural enzymatic repertoire with abiotic reactions. For example, artificial metalloenzymes, which combine the versatile reaction scope of transition metals with the beneficial catalytic features of enzymes, offer an attractive means to engineer new reactions. Three complementary strategies exist: repurposing natural metalloenzymes for abiotic transformations; in silico metalloenzyme (re-)design; and incorporation of abiotic cofactors into proteins. The third strategy offers the opportunity to design a wide variety of artificial metalloenzymes for non-natural reactions. However, many metal cofactors are inhibited by cellular components and therefore require purification of the scaffold protein. This limits the throughput of genetic optimization schemes applied to artificial metalloenzymes and their applicability in vivo to expand natural metabolism. Here we report the compartmentalization and in vivo evolution of an artificial metalloenzyme for olefin metathesis, which represents an archetypal organometallic reaction without equivalent in nature. Building on previous work on an artificial metallohydrolase, we exploit the periplasm of Escherichia coli as a reaction compartment for the ‘metathase’ because it offers an auspicious environment for artificial metalloenzymes, mainly owing to low concentrations of inhibitors such as glutathione, which has recently been identified as a major inhibitor. This strategy facilitated the assembly of a functional metathase in vivo and its directed evolution with substantially increased throughput compared to conventional approaches that rely on purified protein variants. The evolved metathase compares favourably with commercial catalysts, shows activity for different metathesis substrates and can be further evolved in

  3. Directed evolution of artificial metalloenzymes for in vivo metathesis.

    PubMed

    Jeschek, Markus; Reuter, Raphael; Heinisch, Tillmann; Trindler, Christian; Klehr, Juliane; Panke, Sven; Ward, Thomas R

    2016-09-29

    The field of biocatalysis has advanced from harnessing natural enzymes to using directed evolution to obtain new biocatalysts with tailor-made functions. Several tools have recently been developed to expand the natural enzymatic repertoire with abiotic reactions. For example, artificial metalloenzymes, which combine the versatile reaction scope of transition metals with the beneficial catalytic features of enzymes, offer an attractive means to engineer new reactions. Three complementary strategies exist: repurposing natural metalloenzymes for abiotic transformations; in silico metalloenzyme (re-)design; and incorporation of abiotic cofactors into proteins. The third strategy offers the opportunity to design a wide variety of artificial metalloenzymes for non-natural reactions. However, many metal cofactors are inhibited by cellular components and therefore require purification of the scaffold protein. This limits the throughput of genetic optimization schemes applied to artificial metalloenzymes and their applicability in vivo to expand natural metabolism. Here we report the compartmentalization and in vivo evolution of an artificial metalloenzyme for olefin metathesis, which represents an archetypal organometallic reaction without equivalent in nature. Building on previous work on an artificial metallohydrolase, we exploit the periplasm of Escherichia coli as a reaction compartment for the 'metathase' because it offers an auspicious environment for artificial metalloenzymes, mainly owing to low concentrations of inhibitors such as glutathione, which has recently been identified as a major inhibitor. This strategy facilitated the assembly of a functional metathase in vivo and its directed evolution with substantially increased throughput compared to conventional approaches that rely on purified protein variants. The evolved metathase compares favourably with commercial catalysts, shows activity for different metathesis substrates and can be further evolved in

  4. Metathesis in the generation of low-temperature gas in marine shales

    PubMed Central

    2010-01-01

    The recent report of low-temperature catalytic gas from marine shales took on additional significance with the subsequent disclosure of natural gas and low-temperature gas at or near thermodynamic equilibrium in methane, ethane, and propane. It is important because thermal cracking, the presumed source of natural gas, cannot generate these hydrocarbons at equilibrium nor can it bring them to equilibrium over geologic time. The source of equilibrium and the source of natural gas are either the same (generation under equilibrium control) or closely associated. Here we report the catalytic interconversion of hydrocarbons (metathesis) as the source of equilibrium in experiments with Cretaceous Mowry shale at 100°C. Focus was on two metathetic equilibria: methane, ethane, and propane, reported earlier, Q (K = [(C1)*(C3)]/[(C2)2]), and between these hydrocarbons and n-butane, Q* (K = [(C1)*(n-C4)]/[(C2)*(C3)]), reported here for the first time. Two observations stand out. Initial hydrocarbon products are near equilibrium and have maximum average molecular weights (AMW). Over time, products fall from equilibrium and AMW in concert. It is consistent with metathesis splitting olefin intermediates [Cn] to smaller intermediates (fission) as gas generation creates open catalytic sites ([ ]): [Cn] + [ ] → [Cn-m] + [Cm]. Fission rates increasing exponentially with olefin molecular weight could contribute to these effects. AMW would fall over time, and selective fission of [C3] and [n-C4] would draw Q and Q* from equilibrium. The results support metathesis as the source of thermodynamic equilibrium in natural gas. PMID:20142998

  5. Metathesis in the generation of low-temperature gas in marine shales.

    PubMed

    Mango, Frank D; Jarvie, Daniel M

    2010-01-20

    The recent report of low-temperature catalytic gas from marine shales took on additional significance with the subsequent disclosure of natural gas and low-temperature gas at or near thermodynamic equilibrium in methane, ethane, and propane. It is important because thermal cracking, the presumed source of natural gas, cannot generate these hydrocarbons at equilibrium nor can it bring them to equilibrium over geologic time. The source of equilibrium and the source of natural gas are either the same (generation under equilibrium control) or closely associated. Here we report the catalytic interconversion of hydrocarbons (metathesis) as the source of equilibrium in experiments with Cretaceous Mowry shale at 100 degrees C. Focus was on two metathetic equilibria: methane, ethane, and propane, reported earlier, Q (K = [(C(1))*(C(3))]/[(C(2))(2)]), and between these hydrocarbons and n-butane, Q* (K = [(C(1))*(n-C(4))]/[(C(2))*(C(3))]), reported here for the first time. Two observations stand out. Initial hydrocarbon products are near equilibrium and have maximum average molecular weights (AMW). Over time, products fall from equilibrium and AMW in concert. It is consistent with metathesis splitting olefin intermediates [C(n)] to smaller intermediates (fission) as gas generation creates open catalytic sites ([ ]): [C(n)] + [ ] --> [C(n-m)] + [C(m)]. Fission rates increasing exponentially with olefin molecular weight could contribute to these effects. AMW would fall over time, and selective fission of [C(3)] and [n-C(4)] would draw Q and Q* from equilibrium. The results support metathesis as the source of thermodynamic equilibrium in natural gas.

  6. Candle and candle wax containing metathesis and metathesis-like products

    DOEpatents

    Murphy, Timothy A; Tupy, Michael J; Abraham, Timothy W; Shafer, Andy

    2014-04-01

    A wax comprises a metathesis product and/or a product that resembles, at least in part, a product which may be formed from a metathesis reaction. The wax may be used to form articles, for example, candles (container candles, votive candles, and/or a pillar candles), crayons, fire logs, or tarts. The wax commonly includes other components in addition to the metathesis product.

  7. Candle and candle wax containing metathesis and metathesis-like products

    DOEpatents

    Murphy, Timothy A; Tupy, Michael J; Abraham, Timothy W; Shafer, Andy

    2014-12-16

    A wax comprises a metathesis product and/or a product that resembles, at least in part, a product which may be formed from a metathesis reaction. The wax may be used to form articles for example, candles (container candles, votive candles, and/or a pillar candles), crayons, fire logs or tarts. The wax commonly includes other components in addition to the metathesis product.

  8. Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines.

    PubMed

    Pfister, Kai F; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J

    2017-06-01

    Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering.

  9. Biofuel by isomerizing metathesis of rapeseed oil esters with (bio)ethylene for use in contemporary diesel engines

    PubMed Central

    Pfister, Kai F.; Baader, Sabrina; Baader, Mathias; Berndt, Silvia; Goossen, Lukas J.

    2017-01-01

    Rapeseed oil methyl ester (RME) and (bio)ethylene are converted into biofuel with an evenly rising boiling point curve, which fulfills the strict boiling specifications prescribed by the fuel standard EN 590 for modern (petro)diesel engines. Catalyzed by a Pd/Ru system, RME undergoes isomerizing metathesis in a stream of ethylene gas, leading to a defined olefin, monoester, and diester blend. This innovative refining concept requires negligible energy input (60°C) and no solvents and does not produce waste. It demonstrates that the pressing challenge of increasing the fraction of renewables in engine fuel may be addressed purely chemically rather than by motor engineering. PMID:28630908

  10. Olefin recovery via chemical absorption

    SciTech Connect

    Barchas, R.

    1998-06-01

    The recovery of fight olefins in petrochemical plants has generally been accomplished through cryogenic distillation, a process which is very capital and energy intensive. In an effort to simplify the recovery process and reduce its cost, BP Chemicals has developed a chemical absorption technology based on an aqueous silver nitrate solution. Stone & Webster is now marketing, licensing, and engineering the technology. The process is commercially ready for recovering olefins from olefin derivative plant vent gases, such as vents from polyethylene, polypropylene, ethylene oxide, and synthetic ethanol units. The process can also be used to debottleneck C{sub 2} or C{sub 3} splinters, or to improve olefin product purity. This paper presents the olefin recovery imp technology, discusses its applications, and presents economics for the recovery of ethylene and propylene.

  11. Reduce olefin plant fouling

    SciTech Connect

    Martin, J.F. )

    1988-11-01

    Process-side fouling reduces the overall operating efficiency of an olefin plant. The fouling is commonly caused by the formation of organic polymers which also can contain small amounts of inorganic constituents. The fouling is measured reduced if a properly selected antifoulant is used. Specific equipment and areas of the plant affected by process fouling are listed. The fouling tendency in each area is related to the pyrolysis furnace charge and unit operating conditions. To a lesser extent, the design of the plant will dictate which process equipment will experience fouling.

  12. Metathesis transformations of natural products: cross-metathesis of natural rubber and mandarin oil by Ru-alkylidene catalysts.

    PubMed

    Martínez, Araceli; Gutiérrez, Selena; Tlenkopatchev, Mikhail A

    2012-05-18

    This study reports on the degradation of natural rubber (NR) via crossmetathesis with mandarin oil and d-limonene, an abundant compound in essential oils; that were used as chain transfer agents (CTAs) and green solvents. Reactions were performed in the presence of the ruthenium-alkylidene catalysts (PCy₃)₂(Cl)₂Ru=CHPh (I) and (1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) (PCy₃)Cl₂Ru=CHPh (II), respectively. Catalyst II bears an N-heterocyclic carbene ligand (NHC) bounded to the ruthenium atom, which has a strong basic character; therefore it is more active toward trisubstituted olefins in comparison with catalyst I. In both cases, isolated monoterpene-terminated isoprene oligomers were obtained as products of the cross-metathesis degradation of NR. In the presence of catalyst II molecular weight values around M(n) × 10² and yields of 80% were obtained; whereas with catalyst I, the molecular weights of products were about M(n) × 10⁴ with yields ranging 70 to 74%. The composition and yield of NR degradation products were determined by GC/MS (EI) analysis and it was found that the oligomers obtained have primarily one vinyl group and one terpene-monocyclic group at the chain end, with isoprene units A(m) = 2, 3 y 4.

  13. Phosphate Tether-Mediated Ring-Closing Metathesis for the Generation of P-Stereogenic, Z-Configured Bicyclo[7.3.1]- and Bicyclo[8.3.1]phosphates.

    PubMed

    Markley, Jana L; Maitra, Soma; Hanson, Paul R

    2016-02-05

    A phosphate tether-mediated ring-closing metathesis (RCM) study to the synthesis of Z-configured, P-stereogenic bicyclo[7.3.1]- and bicyclo[8.3.1]phosphates is reported. Investigations suggest that C3-substitution, olefin substitution, and proximity of the forming olefin to the bridgehead carbon of the bicyclic affect the efficiency and stereochemical outcome of the RCM event. This study demonstrates the utility of phosphate tether-mediated desymmetrization of C2-symmetric, 1,3-anti-diol-containing dienes in the generation of macrocyclic phosphates with potential synthetic and biological utility.

  14. Alkyne metathesis on the rise.

    PubMed

    Fürstner, Alois

    2013-03-04

    The early years of alkyne metathesis were marked by a somewhat ironic state of affairs: the proposed mechanism was swiftly validated and more than one effective catalyst became available shortly after the discovery of this transformation; surprisingly, however, the impact on synthesis remained very limited for a long period of time. Recent advances, however, suggest that this situation is about to change: the remarkable activity, functional-group tolerance, and reliability of the latest generation of catalysts open the door for highly advanced applications. The resulting (cyclo)alkynes are amenable to numerous postmetathetic transformations, which diversify the product portfolio and bring many different structural motifs into reach. Since the catalysts have also evolved from the glovebox to the benchtop, there should be little barrier left for a wider use of this reaction in organic synthesis.

  15. Recent applications of ring-rearrangement metathesis in organic synthesis

    PubMed Central

    Meshram, Milind; Khedkar, Priti; Banerjee, Shaibal; Deodhar, Deepak

    2015-01-01

    Summary Ring-rearrangement metathesis (RRM) involves multiple metathesis processes such as ring-opening metathesis (ROM)/ring-closing metathesis (RCM) in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008–2014). PMID:26664603

  16. Recent applications of ring-rearrangement metathesis in organic synthesis.

    PubMed

    Kotha, Sambasivarao; Meshram, Milind; Khedkar, Priti; Banerjee, Shaibal; Deodhar, Deepak

    2015-01-01

    Ring-rearrangement metathesis (RRM) involves multiple metathesis processes such as ring-opening metathesis (ROM)/ring-closing metathesis (RCM) in a one-pot operation to generate complex targets. RRM delivers complex frameworks that are difficult to assemble by conventional methods. The noteworthy point about this type of protocol is multi-bond formation and it is an atom economic process. In this review, we have covered literature that appeared during the last seven years (2008-2014).

  17. Chiral Separations

    NASA Astrophysics Data System (ADS)

    Stalcup, A. M.

    2010-07-01

    The main goal of this review is to provide a brief overview of chiral separations to researchers who are versed in the area of analytical separations but unfamiliar with chiral separations. To researchers who are not familiar with this area, there is currently a bewildering array of commercially available chiral columns, chiral derivatizing reagents, and chiral selectors for approaches that span the range of analytical separation platforms (e.g., high-performance liquid chromatography, gas chromatography, supercritical-fluid chromatography, and capillary electrophoresis). This review begins with a brief discussion of chirality before examining the general strategies and commonalities among all of the chiral separation techniques. Rather than exhaustively listing all the chiral selectors and applications, this review highlights significant issues and differences between chiral and achiral separations, providing salient examples from specific classes of chiral selectors where appropriate.

  18. Enantioselective 1,1-arylborylation of alkenes: merging chiral anion phase transfer with Pd catalysis.

    PubMed

    Nelson, Hosea M; Williams, Brett D; Miró, Javier; Toste, F Dean

    2015-03-11

    A palladium-catalyzed three-component coupling of α-olefins, aryldiazonium salts, and bis(pinacolato)diboron affords direct access to chiral benzylic boronic esters. This process is rendered highly enantioselective using an unprecedented example of cooperative chiral anion phase transfer and transition-metal catalysis.

  19. Chiral holmium complex-catalyzed Diels-Alder reaction of silyloxyvinylindoles: stereoselective synthesis of hydrocarbazoles.

    PubMed

    Harada, Shinji; Morikawa, Takahiro; Nishida, Atsushi

    2013-10-18

    The catalytic and asymmetric cycloaddition between 3-[1-(silyloxy)vinyl]indoles and electron-deficient olefins gave substituted hydrocarbazoles in up to 99% yield and 94% ee. This reaction was catalyzed by a novel chiral holmium(III) complex. Alkylation of the cycloadduct gave a tricyclic compound with four continuous chiral centers, one of which was a quaternary carbon.

  20. High-value alcohols and higher-oxidation-state compounds by catalytic Z-selective cross-metathesis

    NASA Astrophysics Data System (ADS)

    Koh, Ming Joo; Khan, R. Kashif M.; Torker, Sebastian; Yu, Miao; Mikus, Malte S.; Hoveyda, Amir H.

    2015-01-01

    Olefin metathesis catalysts provide access to molecules that are indispensable to physicians and researchers in the life sciences. A persisting problem, however, is the dearth of chemical transformations that directly generate acyclic Z allylic alcohols, including products that contain a hindered neighbouring substituent or reactive functional units such as a phenol, an aldehyde, or a carboxylic acid. Here we present an electronically modified ruthenium-disulfide catalyst that is effective in generating such high-value compounds by cross-metathesis. The ruthenium complex is prepared from a commercially available precursor and an easily generated air-stable zinc catechothiolate. Transformations typically proceed with 5.0 mole per cent of the complex and an inexpensive reaction partner in 4-8 hours under ambient conditions; products are obtained in up to 80 per cent yield and 98:2 Z:E diastereoselectivity. The use of this catalyst is demonstrated in the synthesis of the naturally occurring anti-tumour agent neopeltolide and in a single-step stereoselective gram-scale conversion of a renewable feedstock (oleic acid) to an anti-fungal agent. In this conversion, the new catalyst promotes cross-metathesis more efficiently than the commonly used dichloro-ruthenium complexes, indicating that its utility may extend beyond Z-selective processes.

  1. Hafnocene-Based Olefin Polymerizations

    NASA Astrophysics Data System (ADS)

    Diesner, T.; Troll, C.; Rieger, B.

    Zirconocenes have been used for a long time in the field of olefin polymerization using MAO as cocatalyst. The equivalent hafnocenes were seldom used due to a lack of productivity while using MAO activation. In the last few years borane and borate activation has come into the focus of research for olefin polymerization. A variety of different hafnocenes were used to investigate the polymerization mechanism and the different cocatalysts.

  2. Remarkably Efficient Microvawe-Assisted Cross-Metathesis of Lipids in Solvent Free Conditions.

    PubMed

    Ullah, Aman; Arshad, Muhammad

    2017-02-28

    Catalytic transformation of renewable feed stocks into fine chemicals is in high demands and olefin metathesis is one of the sophisticated tools for biomass conversion. Nevertheless, the large scale viability of such processes depends on the conversion efficiency, energy efficiency, catalytic activity, selective conversion into desired products and environmental footprint of the process. Thus, conversions of renewables using simple, swift, and efficient methods are desirable. A microwave-assisted ethenolysis and alkenolysis (using 1-5 hexadiene) of canola oil and methyl esters derived from canola oil (COME) and waste/recycled cooking oil (WOME) was carried out using ruthenium based catalytic systems. A systematic study using 1st and 2nd generation Grubbs (G1, G2) and Hoveyda-Grubbs (HG1 & HG2) catalysts was carried out. Among all ruthenium catalysts, HG2 was found to be highly active in the range of 0.002-0.1 mol% loadings. The conversions proved to be highly efficient with outstanding values of turnover numbers (TONs) and turnover frequencies (TOFs). The TONs for ethenolysis of COME (~1.5 million), direct ethenolysis of canola oil (~0.6 million), more than 1 million for WOME and above 1.6 million for cross metathesis of 1,5-hexadiene with COME were achieved. The ethenolysis of commercial methyl oleate was also performed leading to TONs ~1.2 million and TOFs 20,300 s-1 under microwave conditions.

  3. Organocatalytic atroposelective synthesis of axially chiral styrenes

    NASA Astrophysics Data System (ADS)

    Zheng, Sheng-Cai; Wu, San; Zhou, Qinghai; Chung, Lung Wa; Ye, Liu; Tan, Bin

    2017-05-01

    Axially chiral compounds are widespread in biologically active compounds and are useful chiral ligands or organocatalysts in asymmetric catalysis. It is well-known that styrenes are one of the most abundant and principal feedstocks and thus represent excellent prospective building blocks for chemical synthesis. Driven by the development of atroposelective synthesis of axially chiral styrene derivatives, we discovered herein the asymmetric organocatalytic approach via direct Michael addition reaction of substituted diones/ketone esters/malononitrile to alkynals. The axially chiral styrene compounds were produced with good chemical yields, enantioselectivities and almost complete E/Z-selectivities through a secondary amine-catalysed iminium activation strategy under mild conditions. Such structural motifs are important precursors for further transformations into biologically active compounds and synthetic useful intermediates and may have potential applications in asymmetric synthesis as olefin ligands or organocatalysts.

  4. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, John E.; Herzog, Timothy A.

    1998-01-01

    A metallocene catalyst system for the polymerization of .alpha.-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula ##STR1## wherein: R.sup.1, R.sup.2, and R.sup.3 are independently selected from the group consisting of hydrogen, C.sub.1 to C.sub.10 alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C.sub.1 to C.sub.10 alkyls as a substituent, C.sub.6 to C.sub.15 aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R.sup.8).sub.3 where R.sup.8 is selected from the group consisting of C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; R.sup.4 and R.sup.6 are substituents both having van der Waals radii larger than the van der Waals radii of groups R.sup.1 and R.sup.3 ; R.sup.5 is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E.sup.1, E.sup.2 are independently selected from the group consisting of Si(R.sup.9).sub.2, Si(R.sup.9).sub.2 --Si(R.sup.9).sub.2, Ge(R.sup.9).sub.2, Sn(R.sup.9).sub.2, C(R.sup.9).sub.2, C(R.sup.9).sub.2 --C(R.sup.9).sub.2, where R.sup.9 is C.sub.1 to C.sub.10 alkyl, C.sub.6 to C.sub.15 aryl or C.sub.3 to C.sub.10 cycloalkyl; and the ligand may have C.sub.S or C.sub.1 -symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from .alpha.-olefin monomers.

  5. Stereospecific olefin polymerization catalysts

    DOEpatents

    Bercaw, J.E.; Herzog, T.A.

    1998-01-13

    A metallocene catalyst system is described for the polymerization of {alpha}-olefins to yield stereospecific polymers including syndiotactic, and isotactic polymers. The catalyst system includes a metal and a ligand of the formula shown wherein: R{sup 1}, R{sup 2}, and R{sup 3} are independently selected from the group consisting of hydrogen, C{sub 1} to C{sub 10} alkyl, 5 to 7 membered cycloalkyl, which in turn may have from 1 to 3 C{sub 1} to C{sub 10} alkyls as a substituent, C{sub 6} to C{sub 15} aryl or arylalkyl in which two adjacent radicals may together stand for cyclic groups having 4 to 15 carbon atoms which in turn may be substituted, or Si(R{sup 8}){sub 3} where R{sup 8} is selected from the group consisting of C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; R{sup 4} and R{sup 6} are substituents both having van der Waals radii larger than the van der Waals radii of groups R{sup 1} and R{sup 3}; R{sup 5} is a substituent having a van der Waals radius less than about the van der Waals radius of a methyl group; E{sup 1}, E{sup 2} are independently selected from the group consisting of Si(R{sup 9}){sub 2}, Si(R{sup 9}){sub 2}--Si(R{sup 9}){sub 2}, Ge(R{sup 9}){sub 2}, Sn(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}, C(R{sup 9}){sub 2}--C(R{sup 9}){sub 2}, where R{sup 9} is C{sub 1} to C{sub 10} alkyl, C{sub 6} to C{sub 15} aryl or C{sub 3} to C{sub 10} cycloalkyl; and the ligand may have C{sub S} or C{sub 1}-symmetry. Preferred metals are selected from the group consisting of group III, group IV, group V or lanthanide group elements. The catalysts are used to prepare stereoregular polymers including polypropylene from {alpha}-olefin monomers.

  6. Chiral mixtures

    NASA Astrophysics Data System (ADS)

    Petitjean, Michel

    2002-08-01

    An index evaluating the amount of chirality of a mixture of colored random variables is defined. Properties are established. Extreme chiral mixtures are characterized and examples are given. Connections between chirality, Wasserstein distances, and least squares Procrustes methods are pointed out.

  7. Bond Energies in Models of the Schrock Metathesis Catalyst

    SciTech Connect

    Vasiliu, Monica; Li, Shenggang; Arduengo, Anthony J.; Dixon, David A.

    2011-06-23

    Heats of formation, adiabatic and diabatic bond dissociation energies (BDEs) of the model Schrock-type metal complexes M(NH)(CRR)(OH)₂ (M = Cr, Mo, W; CRR = CH₂, CHF, CF₂) and MO₂(OH)₂ compounds, and Brønsted acidities and fluoride affinities for the M(NH)(CH₂)(OH) ₂ transition metal complexes are predicted using high level CCSD(T) calculations. The metallacycle intermediates formed by reaction of C₂H4 with M(NH)-(CH₂)(OH)2 and MO₂(OH)₂ are investigated at the same level of theory. Additional corrections were added to the complete basis set limit to obtain near chemical accuracy ((1 kcal/mol). A comparison between adiabatic and diabatic BDEs is made and provides an explanation of trends in the BDEs. Electronegative groups bonded on the carbenic carbon lead to less stable Schrock-type complexes as the adiabatic BDEs ofMdCF₂ andMdCHF bonds are much lower than theMdCH₂ bonds. The Cr compounds have smaller BDEs than theWorMo complexes and should be less stable. Different M(NH)(OH)₂(C₃H₆) and MO(OH)₂(OC₂H4) metallacycle intermediates are investigated, and the lowest-energy metallacycles have a square pyramidal geometry. The results show that consideration of the singlet_triplet splitting in the carbene in the initial catalyst as well as in the metal product formed by the retro [2+2] cycloaddition is a critical component in the design of an effective olefin metathesis catalyst in terms of the parent catalyst and the groups being transferred.

  8. STERIC EFFECTS IN ALPHA-OLEFIN REACTIVITY

    DTIC Science & Technology

    successfully applied to alpha - olefins to correlate reaction rates with steric effects and to explain, in part, the difficulty of obtaining desirable polymers from these olefins ....Addition reactions to the double bond of a series of sterically-hindered alpha - olefins have been carried out. The kinetics of these reaction were...measured and the rates of reaction correlated with the steric effects present in the olefin . A theory known as "Newman’s rule of six" has been

  9. 21 CFR 177.1520 - Olefin polymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Olefin polymers. 177.1520 Section 177.1520 Food and... CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1520 Olefin polymers. The olefin polymers listed in paragraph...

  10. Iron(II)-catalyzed intramolecular aminohydroxylation of olefins with functionalized hydroxylamines.

    PubMed

    Liu, Guan-Sai; Zhang, Yong-Qiang; Yuan, Yong-An; Xu, Hao

    2013-03-06

    A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.

  11. Enantioseparation of glycyl-dipeptides by CEC using particle-loaded monoliths prepared by ring-opening metathesis polymerization (ROMP).

    PubMed

    Gatschelhofer, Christina; Schmid, Martin G; Schreiner, Karin; Pieber, Thomas R; Sinner, Frank M; Gübitz, Gerald

    2006-11-30

    Novel particle-loaded monolithic capillary electrochromatography (CEC) phases for chiral separations were prepared via ring-opening metathesis polymerization (ROMP) within the confines of fused silica columns with 200 microm i.d. using norborn-2-ene (NBE), 1,4,4a,5,8,8a-hexahydro-1,4,5,8,exo,endo-dimethanonaphthalene (DMN-H6) as monomers, 2-propanol and toluene as porogens, RuCl2(PCy3)2(CHPh) as initiator and silica-based particles containing the chiral selector. By suspending silica particles bearing the chiral selector in the polymerization mixture, particle-based monoliths are easily prepared. This approach has several advantages compared to particle-based separation media: (i) the concept of particle-based monoliths is broadly applicable, as any silica-based chiral phase can be used; (ii) they are inexpensive to prepare; and (iii) the manufacturing process is very simple, no sophisticated packing procedures or the preparation of end frits are required. To show the usefulness of this concept for chiral CEC, the chiral separation performance of particle-loaded CEC monoliths bearing teicoplanin aglycone, chemically bonded to 3 microm silica gel, was investigated for a set of glycyl-dipeptides. Particle-loaded ROMP CEC monoliths showed good separation performance for glycyl-dipeptides.

  12. A kinetic, mechanistic, and molecular mechanics investigation of olefin insertion into organoactinide-hydride bonds. Metal, olefin, ancillary ligand, and diastereoselection effects

    SciTech Connect

    Lin, Zerong; Marks, T.J. )

    1990-07-04

    This contribution reports a kinetic/mechanistic/stereochemical/molecular mechanics study of olefin insertion into the actinide-hydrogen bonds of Cp{prime}{sub 2}An(H)(OR) complexes (Cp{prime} = {eta}{sup 5}-(CH{sub 3}){sub 5}C{sub 5}; An = Th, U; R = achiral or chiral alkyl group). For the reaction Cp{prime}{sub 2}An(H)(O-t-Bu) + cyclohexene (An = Th), the rate law is first order in organoactinide and first order in olefin. For Cp{prime}{sub 2}Th(H)(OCH(t-Bu){sub 2}) + 1-hexene, k{sub Th{minus}H}/k{sub Th{minus}D} = 1.3 (2). A molecular mechanics/ molecular graphics analysis suggests that the sterically most favorable direction of olefin approach toward the actinide center is between the U-H and U-O bonds rather than from the side. These results provide additional insight into ancillary ligand effects on the kinetics of organo-f-element-catalyzed olefin hydrogenation.

  13. Chiral superconductors.

    PubMed

    Kallin, Catherine; Berlinsky, John

    2016-05-01

    Chiral superconductivity is a striking quantum phenomenon in which an unconventional superconductor spontaneously develops an angular momentum and lowers its free energy by eliminating nodes in the gap. It is a topologically non-trivial state and, as such, exhibits distinctive topological modes at surfaces and defects. In this paper we discuss the current theory and experimental results on chiral superconductors, focusing on two of the best-studied systems, Sr2RuO4, which is thought to be a chiral triplet p-wave superconductor, and UPt3, which has two low-temperature superconducting phases (in zero magnetic field), the lower of which is believed to be chiral triplet f-wave. Other systems that may exhibit chiral superconductivity are also discussed. Key signatures of chiral superconductivity are surface currents and chiral Majorana modes, Majorana states in vortex cores, and the possibility of half-flux quantum vortices in the case of triplet pairing. Experimental evidence for chiral superconductivity from μSR, NMR, strain, polar Kerr effect and Josephson tunneling experiments are discussed.

  14. Production of diesel fuel from light olefins

    SciTech Connect

    Tabak, S.A.; Krambeck, F.J.

    1986-03-01

    Mobile Research and Development Corporation has developed a catalytic process for converting light olefinic compounds to high quality gasoline and distillate. The process has been named Mobil Olefin to Gasoline and Distillate (MOGD) Process. Based on the Mobile zeolite catalyst ZSM-5, light olefins can be shape selectively oligomerized to higher molecular weight iso-olefins. In the gasoline boiling range, these olefins have a high octane number and for the diesel fuel range product a high cetane number and low pour point following hydrogenation. Through normally designed to process propylene or butylene, MOGD is applicable to a wide range of feed streams ranging from ethylene to 400/sup 0/F endpoint olefinic naphtha. The process has been tested using commercially-produced catalyst in refinery scale equipment.

  15. Generation of stoichiometric ethylene and isotopic derivatives and application in transition-metal-catalyzed vinylation and enyne metathesis.

    PubMed

    Min, Geanna K; Bjerglund, Klaus; Kramer, Søren; Gøgsig, Thomas M; Lindhardt, Anders T; Skrydstrup, Troels

    2013-12-16

    Ethylene is one of the most important building blocks in industry for the production of polymers and commodity chemicals. (13)C- and D-isotope-labeled ethylenes are also valuable reagents with applications ranging from polymer-structure determination, reaction-mechanism elucidation to the preparation of more complex isotopically labeled compounds. However, these isotopic derivatives are expensive, and are flammable gases, which are difficult to handle. We have developed a method for the controlled generation of ethylene and its isotopic variants including, for the first time, fully isotopically labeled ethylene, from simple alkene precursors by using Ru catalysis. Applying a two-chamber reactor allows both the synthesis of ethylene and its immediate consumption in a chemical transformation permitting reactions to be performed with only stoichiometric amounts of this two carbon olefin. This was demonstrated in the Ni-catalyzed Heck reaction with aryl triflates and benzyl chlorides, as well as Ru-mediated enyne metathesis.

  16. Synergy between Two Metal Catalysts: A Highly Active Silica-Supported Bimetallic W/Zr Catalyst for Metathesis of n-Decane.

    PubMed

    Samantaray, Manoja K; Dey, Raju; Kavitake, Santosh; Abou-Hamad, Edy; Bendjeriou-Sedjerari, Anissa; Hamieh, Ali; Basset, Jean-Marie

    2016-07-13

    A well-defined, silica-supported bimetallic precatalyst [≡Si-O-W(Me)5≡Si-O-Zr(Np)3] (4) has been synthesized for the first time by successively grafting two organometallic complexes [W(Me)6 (1) followed by ZrNp4 (2)] on a single silica support. Surprisingly, multiple-quantum NMR characterization demonstrates that W and Zr species are in close proximity to each other. Hydrogenation of this bimetallic catalyst at room temperature showed the easy formation of zirconium hydride, probably facilitated by tungsten hydride which was formed at this temperature. This bimetallic W/Zr hydride precatalyst proved to be more efficient (TON = 1436) than the monometallic W hydride (TON = 650) in the metathesis of n-decane at 150 °C. This synergy between Zr and W suggests that the slow step of alkane metathesis is the C-H bond activation that occurs on Zr. The produced olefin resulting from a β-H elimination undergoes easy metathesis on W.

  17. Make olefins from syn gas

    SciTech Connect

    Rao, V.U.S.; Gormley, R.J.

    1980-11-01

    The medium pore zeolite ZSM-5 can be made within a wide range of values of the ratio SiO/sub 2//Al/sub 2/O/sub 3/. The crystal structures of ZSM-5 and Silicalite appear to be very similar. However, Silicalite has essentially no Al. Hence it appears that Silicalite is the limiting form of ZSM-5 when the Al concentration is vanishingly small. A comparison of the properties of ZSM-5 and Silicalite is shown. Silicalite provides an interesting contrast to ZSM-5 owing to the lack of acidity in the former. In comparing products from catalysts based on ZSM-5 and Silicalite, one can discern reactions which result from the acid function in ZSM-5. Our studies on bifunctional catalysts based on ZSM-5 and Silicalite were performed on zeolites or molecular sieves impregnated with Fe and/or Co. The aim was to convert synthesis gas (CO + H/sub 2/), which can be derived from the gasification of coal, to olefins or gasoline. In the case of the ZSM-based catalyst containing Fe, the transition metal catalyzes the hydrogenation of CO, and the acid function of the zeolite catalyzes the conversion of the oxygenates and olefins in the product to aromatics, resulting in a high octane gasoline product. Recent work from our laboratory has clearly shown that if Silicalite is used instead of ZSM-5 as the support, the production of aromatics is almost completely suppressed, and the product stream is rich in olefins. In the present article, molecular sieve based catalysts that can proide olefins are discussed, and some aspects of gasoline production using zeolite based catalysts as well as the control of shift activity are also being considered. 4 tables.

  18. Chiral plasmonics

    PubMed Central

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-01-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes. PMID:28560336

  19. Chiral plasmonics.

    PubMed

    Hentschel, Mario; Schäferling, Martin; Duan, Xiaoyang; Giessen, Harald; Liu, Na

    2017-05-01

    We present a comprehensive overview of chirality and its optical manifestation in plasmonic nanosystems and nanostructures. We discuss top-down fabricated structures that range from solid metallic nanostructures to groupings of metallic nanoparticles arranged in three dimensions. We also present the large variety of bottom-up synthesized structures. Using DNA, peptides, or other scaffolds, complex nanoparticle arrangements of up to hundreds of individual nanoparticles have been realized. Beyond this static picture, we also give an overview of recent demonstrations of active chiral plasmonic systems, where the chiral optical response can be controlled by an external stimulus. We discuss the prospect of using the unique properties of complex chiral plasmonic systems for enantiomeric sensing schemes.

  20. Isotopic chirality

    SciTech Connect

    Floss, H.G.

    1994-12-01

    This paper deals with compounds that are chiral-at least in part, due to isotope substitution-and their use in tracing the steric course of enzyme reaction in vitro and in vivo. There are other applications of isotopically chiral compounds (for example, in analyzing the steric course of nonenzymatic reactions and in probing the conformation of biomolecules) that are important but they will not be discussed in this context.

  1. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOEpatents

    Sen, A.; Jiang, Z.

    1996-05-28

    The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

  2. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOEpatents

    Sen, Ayusman; Jiang, Zhaozhong

    1996-01-01

    The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

  3. Features and Application in Asymmetric Catalysis of Chiral Phosphine-Phosphite Ligands.

    PubMed

    Pizzano, Antonio

    2016-12-01

    Chiral phosphine-phosphites are a class of ligands for asymmetric catalysis characterized by two coordinating functionalities with different electronic properties. These ligands also possess a highly modular structure and, due to versatile synthetic processes, they can be tuned precisely in the catalyst optimization process. Research regarding the application of these ligands in several enantioselective catalytic processes has provided outstanding results in a good number of them. These processes include not only Rh catalyzed reactions, such as olefin hydrogenation and hydroformylation, but also other reactions, such as hydrogenation of olefins and imines by Ru complexes, of imines and N-heterocycles by Ir derivatives, allyl alkylation or conjugate addition by Cu catalysts, or hydrocyanation of olefins by Ni ones. Overall, the use of these ligands has led to the preparation of a wide variety of chiral building blocks with high enantiomeric excess. Therefore, phosphine-phosphites have become in an important class of ligands in asymmetric catalysis.

  4. A novel chiral yttrium complex with a tridentate linked amido-indenyl ligand for intramolecular hydroamination.

    PubMed

    Chai, Zhuo; Hua, Dezhi; Li, Kui; Chu, Jiang; Yang, Gaosheng

    2014-01-07

    A new chiral silicon-linked tridentate amido-indenyl ligand was developed from indene and enantiopure 1,2-cyclohexanediamine. Its yttrium complex was synthesized, characterized and applied to efficiently catalyze the intramolecular hydroamination of non-activated olefins with up to 97% ee.

  5. An alkyne metathesis-based route toortho-dehydrobenzannulenes

    SciTech Connect

    Miljanic, Ognjen S.; Vollhardt, Peter C.; Whitener, Glenn D.

    2002-11-07

    An application of alkyne metathesis to 1,2-di(prop-1-ynyl)arenes, producing dehydrobenzannulenes, is described. An efficient method for selective Sonogashira couplings of bromoiodoarenes under conditions of microwave irradiation is also reported.

  6. Methods for synthesis of olefins and derivatives

    DOEpatents

    Burk, Mark J.; Pharkya, Priti; Van Dien, Stephen J.; Burgard, Anthony P.; Schilling, Christophe H.

    2016-06-14

    The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

  7. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    SciTech Connect

    Albright, L.F.; Kranz, K.E.; Masters, K.R.

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  8. Understanding the desensitizing mechanism of olefin in explosives: shear slide of mixed HMX-olefin systems.

    PubMed

    Zhang, Chaoyang; Cao, Xia; Xiang, Bin

    2012-04-01

    We simulated the shear slide behavior of typical mixed HMX-olefin systems and the effect of thickness of olefin layers (4-22 Å) on the behavior at a molecular level by considering two cases: bulk shear and interfacial shear. The results show that: (1) the addition of olefin into HMX can reduce greatly the shear sliding barriers relative to the pure HMX in the two cases, suggesting that the desensitizing mechanism of olefin is controlled dominantly by its good lubricating property; (2) the change of interaction energy in both systoles of shear slide is strongly dominated by van der Waals interaction; and (3) the thickness of olefin layers in the mixed explosives can influence its desensitizing efficiency. That is, the excessive thinness of olefin layers in the mixed explosive systems, for example, several angstroms, can lead to very high sliding barriers.

  9. Enantioselective Cyclopropanation of a Wide Variety of Olefins Catalyzed by Ru(II)-Pheox Complexes.

    PubMed

    Chanthamath, Soda; Iwasa, Seiji

    2016-10-18

    The transition-metal-catalyzed asymmetric cyclopropanation of olefins with diazoacetates has become one of the most important methods for the synthesis of optically active cyclopropane derivatives, which are key pharmaceutical building blocks and present in a large number of natural products. To date, significant progress has been made in this area of research, and efficient stereocontrolled synthetic approaches to cyclopropane derivatives have been developed using rhodium, ruthenium, copper, and cobalt catalysts. However, the vast majority of these strategies are limited to electron-rich olefins, such as styrene derivatives, due to the electrophilicity of the metal-carbene intermediates generated from the reaction of the metal with the diazo compound. Recently, the D2-symmetric Co(II)-phophyrin complexes developed by Zhang et al. were shown to be the most efficient catalysts for the asymmetric cyclopropanation of electron-deficient olefins. This catalytic system is mechanistically distinct from the previous rhodium and copper catalytic systems, proceeding via radical intermediates. However, the asymmetric cyclopropanation of vinyl carbamates, allenes, and α,β-unsaturated carbonyl compounds has rarely been reported. Therefore, the development of new powerful catalysts for the asymmetric cyclopropanation of a wide range of olefinic substrates is the next challenge in this field. In this Account, we summarize our recent studies on the Ru(II)-Pheox-catalyzed asymmetric cyclopropanation of various olefins, including vinyl carbamates, allenes, and α,β-unsaturated carbonyl compounds. We demonstrate that the developed catalytic system effectively promotes the asymmetric cyclopropanation of a wide variety of olefins to produce the desired cyclopropane products in high yields with excellent stereocontrol. The use of succinimidyl-, ketone-, and ester-functionalized diazoacetates as carbene sources was found to be crucial for the high stereoselectivity of the

  10. Prebiotic chirality

    NASA Astrophysics Data System (ADS)

    Mekki-Berrada, Ali

    Bringing closer phospholipids each other on a bilayer of liposome, causes their rotation around their fatty acids axis, generating a force which brings closer the two sheets of the bilayer. In this theoretical study I show that for getting the greater cohesion of the liposome, by these forces, the serine in the hydrophilic head must have a L chirality. In the case where the hydrophilic head is absent amino acids with L chirality could contribute to this cohesion by taking the place of L-serine. Some coenzymes having a configuration similar to ethanolamine may also contribute. This is the case of pyridoxamine, thiamine and tetrahydrofolic acid. The grouping of amino acids of L chirality and pyridoxamine on the wall could initialize the prebiotic metabolism of these L amino acids only. This would explain the origin of the homo-chirality of amino acids in living world. Furthermore I show that in the hydrophilic head, the esterification of glycerol-phosphate by two fatty acids go through the positioning of dihydroxyacetone-phosphate and L-glyceraldehyde-3-phosphate, but not of D-glyceraldehyde-3-phosphate, prior their hydrogenation to glycerol-3- phosphate. The accumulation of D-glyceraldehyde-3-phosphate in the cytoplasm displace the thermodynamic equilibria towards the synthesis of D-dATP from D-glyceraldehyde-3-phosphate, acetaldehyde and prebiotic adenine, a reaction which does not require a coenzyme in the biotic metabolism. D-dATP and thiamine, more prebiotic metabolism of L-amino acids on the wall, would initialize D-pentoses phosphate and D-nucleotides pathways from the reaction of D-glyceraldehyde-3-phosphate + dihydroxyacetone-phosphate + prebiotic nucleic bases. The exhaustion of the prebiotic glyceraldehyde (racemic) and the nascent biotic metabolism dominated by D-glyceraldehyde-3-phosphate, would explain the origin of homo-chirality of sugars in living world. References: http://en.wikiversity.org/wiki/Prebiotic_chirality

  11. Chiral Polymers.

    DTIC Science & Technology

    1984-10-01

    TITLE (mid Subttlo) 񓂬-JS. TYPE OF REPORT & PERIOD COVERED CHIRAL POLYMERS /~O~~ R E~NNE 7. AUTHOR(e) 11. CONTRACT OR GRANT NUNSIER(e) J. K. Stille...acrylamide monomer containing a chiral 1,3-dioxane unit as well as both racemic and ( R )-6.-methyl ene-vi-methyl -7-butyrol actone were synthesi zed...or ( R )-propylene oxide (10)6. The key step in this synthesis is the palladium catalyzed carbonylation of 4-bromopent-4-en-2-ol. Thus, either racemic or

  12. Metathesis depolymerization for removable surfactant templates.

    SciTech Connect

    Zifer, Thomas; Wheeler, David Roger; Rahimian, Kamayar; McElhanon, James Ross; Long, Timothy Michael; Jamison, Gregory Marks; Loy, Douglas Anson; Kline, Steven R.; Simmons, Blake Alexander

    2005-03-01

    Current methodologies for the production of meso- and nanoporous materials include the use of a surfactant to produce a self-assembled template around which the material is formed. However, post-production surfactant removal often requires centrifugation, calcination, and/or solvent washing which can damage the initially formed material architecture(s). Surfactants that can be disassembled into easily removable fragments following material preparation would minimize processing damage to the material structure, facilitating formation of templated hybrid architectures. Herein, we describe the design and synthesis of novel cationic and anionic surfactants with regularly spaced unsaturation in their hydrophobic hydrocarbon tails and the first application of ring closing metathesis depolymerization to surfactant degradation resulting in the mild, facile decomposition of these new compounds to produce relatively volatile nonsurface active remnants.

  13. Quaternary Stereogenic Centers through Enantioselective Heck Arylation of Acyclic Olefins with Aryldiazonium Salts: Application in a Concise Synthesis of (R)-Verapamil.

    PubMed

    Oliveira, Caio C; Pfaltz, Andreas; Correia, Carlos Roque Duarte

    2015-11-16

    We describe herein a highly regio- and enantioselective Pd-catalyzed Heck arylation of unactivated trisubstituted acyclic olefins to provide all-carbon quaternary stereogenic centers. Chiral N,N ligands of the pyrimidine- and pyrazino-oxazoline class were developed for that purpose, providing the desired products in good to high yields with enantiomeric ratios up to >99:1. Both linear and branched substituents on the olefins were well-tolerated. The potential of this new method is demonstrated by the straightforward synthesis of several O-methyl lactols and lactones containing quaternary stereocenters, together with a concise enantioselective total synthesis of the calcium channel blocker verapamil.

  14. Synthesis and conformational study of a novel macrocyclic chiral(salen) ligand and its uranyl and Mn complexes.

    PubMed

    Amato, Maria E; Ballistreri, Francesco P; Pappalardo, Andrea; Tomaselli, Gaetano A; Toscano, Rosa M

    2010-03-09

    A novel chiral macrocyclic ligand incorporating a chiral salen moiety into a framework containing two biphenyl units was synthesized. Structural properties and conformational aspects of the free ligand and an UO2 complex were studied by using NMR spectroscopy in solution and MM calculations. The Mn(III) complex was tested as catalyst in enantioselective oxidation of prochiral unfunctionalized olefins to the corresponding optically active epoxides under very mild conditions.

  15. Selective conversion of bio-oil to light olefins: controlling catalytic cracking for maximum olefins.

    PubMed

    Gong, Feiyan; Yang, Zhi; Hong, Chenggui; Huang, Weiwei; Ning, Shen; Zhang, Zhaoxia; Xu, Yong; Li, Quanxin

    2011-10-01

    Light olefins are the basic building blocks for the petrochemical industry. In this work, selective production of light olefins from catalytic cracking of bio-oil was performed by using the La/HZSM-5 catalyst. With a nearly complete conversion of bio-oil, the maximum yield reached 0.28±0.02 kg olefins/(kg bio-oil), which was close to that from methanol. Addition of La into zeolite efficiently changed the total acid amount of HZSM-5, especially the acid distribution among the strong, medium and weak acid sites. A moderate increase of the number of the medium acid sites effectively enhanced the olefins selectivity and improved the catalyst stability. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the conversion of bio-oil to light olefins was also discussed.

  16. Chiral streamers

    SciTech Connect

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya

    2015-10-15

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  17. Chiral streamers

    NASA Astrophysics Data System (ADS)

    Zou, Dandan; Cao, Xin; Lu, Xinpei; Ostrikov, Kostya Ken

    2015-10-01

    The interaction of time-varying electromagnetic fields and solid, liquid, and gaseous matter may lead to electrical breakdown phenomena through the excitation of ionization waves or streamers that control the dynamics of localized plasma propagation through the media. The streamers usually propagate along straight lines, either between random points in space or along a certain direction in a guided mode. Here, we report on a new type of plasma discharges with the regular helical propagation pattern driven by a pulsed dc voltage in nitrogen at sub-atmospheric-pressure conditions. The helical guided streamers, named chiral streamers or chi-streamers, are excited without any external magnetic fields, which commonly cause helical plasma motions. We also demonstrate a hybrid propagation mode involving the interchangeable chiral streamers and the straight-line propagating plasmas. High-speed, time-resolved optical imaging reveals that the chiral streamers and the hybrid patterns are made of spatially localized discrete plasma bullets, similar to the straight-line guided streamers. These results may enable effective control of propagation of confined plasmas and electromagnetic energy along pre-determined, potentially deterministic paths, which have important implications for the development of next-generation plasma-based radiation sources, communication devices, and medical treatments.

  18. Beta-H transfer from the metallacyclobutane: a key step in the deactivation and byproduct formation for the well-defined silica-supported rhenium alkylidene alkene metathesis catalyst.

    PubMed

    Leduc, Anne-Marie; Salameh, Alain; Soulivong, Daravong; Chabanas, Mathieu; Basset, Jean-Marie; Copéret, Christophe; Solans-Monfort, Xavier; Clot, Eric; Eisenstein, Odile; Böhm, Volker P W; Röper, Michael

    2008-05-14

    The surface complex [([triple bond]SiO)Re([triple bond]CtBu)(=CHtBu)(CH2tBu)] (1) is a highly efficient propene metathesis catalyst with high initial activities and a good productivity. However, it undergoes a fast deactivation process with time on stream, which is first order in active sites and ethene. Noteworthy, 1-butene and pentenes, unexpected products in the metathesis of propene, are formed as primary products, in large amount relative to Re (>1 equiv/Re), showing that their formation is not associated with the formation of inactive species. DFT calculations on molecular model systems show that byproduct formation and deactivation start by a beta-H transfer trans to the weak sigma-donor ligand (siloxy) at the metallacyclobutane intermediate having a square-based pyramid geometry. This key step has an energy barrier slightly higher than that calculated for olefin metathesis. After beta-H transfer, the most accessible pathway is the insertion of ethene in the Re-H bond. The resulting pentacoordinated trisperhydrocarbyl complex rearranges via either (1) alpha-H abstraction yielding the unexpected 1-butene byproduct and the regeneration of the catalyst or (2) beta-H abstraction leading to degrafting. These deactivation and byproduct formation pathways are in full agreement with the experimental data.

  19. Synthesis, characterization and insights into stable and well organized hexagonal mesoporous zinc-doped alumina as promising metathesis catalysts carrier.

    PubMed

    Abidli, Abdelnasser; Hamoudi, Safia; Belkacemi, Khaled

    2015-06-07

    A series of highly ordered hexagonal mesoporous alumina and zinc-modified mesoporous alumina samples are synthesized via a sol-gel method through an evaporation-induced self-assembly process using Pluronic F127 as nonionic templating agent and several aluminum precursors. The process was mediated using several carboxylic acids along with hydrochloric acid in ethanol. Successful impregnation of ZnCl2 was achieved while maintaining the ordered structure. The surface and textural properties of the materials were investigated. N2-physisorption analysis revealed a BET surface area of 394 m(2) g(-1) and a pore volume around 0.55 cm(3) g(-1). Moreover, small-angle XRD diffraction patterns highlighted the well-organized hexagonal structure even upon the incorporation of zinc chloride. The organized-structure arrangement was further confirmed by transmission electron microscopy (TEM) analysis. The Zn/Al composition of the final materials was confirmed by EDX and XPS analysis, and the zinc amount incorporated was analyzed by ICP. Furthermore, the surface modification with zinc chloride impregnation was analyzed by XPS, (1)H and (27)Al MAS-NMR and FTIR spectroscopic techniques. In addition, the effects of synthesis conditions and the mechanism of the mesostructure formation were explored. The catalytic activity of several methyltrioxorhenium (MTO)-based catalysts supported on these hexagonal mesoporous alumina materials was tested for methyl oleate self-metathesis. The results showed improved kinetics using hexagonal alumina in comparison to those using wormhole-like alumina counterparts. This behavior could be attributed to better mass transfer features of hexagonal mesoporous alumina. The prepared materials with desirable pore size and structure are suitable candidates as catalyst supports for metathesis of bulky functionalized olefins and other catalytic transformations due to their enhanced Lewis acidity and more uniform pore networks favoring enhanced and selective mass

  20. Palladium(II)-catalyzed isospecific alternating copolymerization of aliphatic {alpha}-olefins with carbon monoxide and isospecific alternating isomerization cooligomerization of a 1,2-disubstituted olefin with carbon monoxide. Synthesis of novel, optically active, isotatic 1,4- and 1,5-polyketones

    SciTech Connect

    Jiang, Z.; Sen, A.

    1995-04-26

    The compound [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, 1 [Me-DUPHOS = 1,2-bis(2,5-dimethylphospholano)-benzene], has been found to be an effective catalyst for the highly enantioselective, alternating copolymerization of aliphatic {alpha}-olefins with carbon monoxide to form optically active, isotactic polymers. The {alpha}-olefin--carbon monoxide copolymers, as synthesized in CH{sub 3}NO{sub 2}/CH{sub 3}OH, had a mixture of 1,4-ketone and spiroketal repeating units in the backbone. The interchange between 1,4-keto and spiroketal units was observed even in the absence of any added metal catalyst. The temperature dependence of the molar optical rotation of the isotactic pure poly(1,4-ketone)s indicated that the chirality of the copolymers was due to the presence of stereogenic tertiary carbons in the polymer backbone rather than due to polymer conformation. The degree of enantioselectivity in the formation of chiral, isotactic propylene-carbon monoxide copolymer was found to be > 90{degree} (as determined by NMR spectroscopy using a chiral NMR shift reagent). The isotactic {alpha}-olefin-carbon monoxide copolymers serve as excellent starting materials for the synthesis of other classes of chiral polymers. 14 refs., 10 figs., 1 tab.

  1. 40 CFR 721.10672 - Sodium olefin sulfonate derivative (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Sodium olefin sulfonate derivative... Specific Chemical Substances § 721.10672 Sodium olefin sulfonate derivative (generic). (a) Chemical... as sodium olefin sulfonate derivative (PMNs P-09-447 and P-09-448) are subject to reporting...

  2. Olefins can limit desulfurization of reformer feedstock

    SciTech Connect

    Ali, S.A.; Anabtawi, J.A.

    1995-07-03

    Pilot plant studies have shown that the presence of even very small amounts of olefins may limit the desulfurization of reformer feedstocks to trace levels. Engineers at the Research Institute of King Fahd University of Petroleum and Minerals observed under typical industrial conditions the recombination reaction of olefins with hydrogen sulfide to form mercaptans. The results indicate that the advantage of using highly active (third generation) CoMo hydrotreating catalysts can be masked by these reactions if the olefins are not saturated. The trend in naphtha reforming is to use high-rhenium, bimetallic catalysts that display less resistance to sulfur than do balanced Pt-Re catalysts. Due consideration, therefore, should be given to these undesirable recombination reactions while designing hydrotreaters and selecting hydrodesulfurization (HDS) and reforming catalysts. The paper discusses catalysts and feedstock tests, catalyst activity, temperature effects, space velocity, feedstock effect, catalyst performance, and recommendations.

  3. A Practical Solution to Stereodefined Tetrasubstituted Olefins.

    PubMed

    Dai, Jianxin; Wang, Minyan; Chai, Guobi; Fu, Chunling; Ma, Shengming

    2016-03-02

    Olefins, compounds with a carbon-carbon double bond, are of fundamental importance, and stereodefined construction of tetrasubstituted carbon-carbon double bond is a significant challenge. Here we show a unique and practical method for the preparation of stereodefined, fully substituted olefins via conjugate addition of organozinc reagents to readily available 2,3-allenals. Through mechanistic studies, it is confirmed that the geometry of the newly formed double bond is controlled by unique regiospecific oxygen-protonation of the enolate intermediates, generating 1,3-alkadienols. Such alkadienols would undergo a concerted 1,5-H-transfer reaction via a six-membered transition state to ensure the configuration of the carbon-carbon double bond in the final products. Using the readily available organozinc reagents and 2,3-allenals provides a very rapid access to a wide range of tetrasubstituted olefins with defined stereochemistry, bearing an extremely versatile aldehyde functionality.

  4. Olefins from methanol by modified zeolites

    SciTech Connect

    Inui, T.; Takegami, Y.

    1982-11-01

    Compares the effects of modified catalysts (ZSM-34 and ZSM-5 class zeolites) on methanol conversion to olefins (MTO) with regard to olefin selectivity and cost. Presents tables with prices of olefins in the US and Japan; comparison of methanol-cracking with naphtha cracking; methanol conversion data for Type-1, Type-II and reference catalysts; hydrocarbon distribution from MTO processes; and speculative economics for MTO processes of Concept-1 and 2. Diagrams the proposed MTO process scheme. Scanning electron micrographs of the zeolite catalysts are shown. Graphs indicate the change of ethylene prices in the US since 1978 and forecast ethylene prices in several countries. Concludes that the prices of ethylene for both MTO processes examined compare favorably with products of conventional processes.

  5. (Z)-Selective Takai olefination of salicylaldehydes

    PubMed Central

    Galloway, Warren R J D; Sore, Hannah F; Goodman, Jonathan M

    2017-01-01

    The Takai olefination (or Takai reaction) is a method for the conversion of aldehydes to vinyl iodides, and has seen widespread implementation in organic synthesis. The reaction is usually noted for its high (E)-selectivity; however, herein we report the highly (Z)-selective Takai olefination of salicylaldehyde derivatives. Systematic screening of related substrates led to the identification of key factors responsible for this surprising inversion of selectivity, and enabled the development of a modified mechanistic model to rationalise these observations. PMID:28326141

  6. Iron-catalyzed aminohydroxylation of olefins.

    PubMed

    Williamson, Kevin S; Yoon, Tehshik P

    2010-04-07

    We have discovered that N-sulfonyl oxaziridines react with a broad range of olefins in the presence of iron salts to afford 1,3-oxazolidines. This process provides access to 1,2-aminoalcohols with the opposite sense of regioselectivity produced from the copper-catalyzed oxyamination previously reported by our laboratories. Thus, either regioisomeric form of 1,2-aminoalcohols can easily be obtained from the reaction of oxaziridines with olefins, and the sense of regioselectivity can be controlled by the appropriate choice of inexpensive, nontoxic, first-row transition-metal catalyst.

  7. Fully stereocontrolled syntheses of 3-oxacarbacyclin and carbacyclin by the conjugate addition-azoalkene-asymmetric olefination strategy.

    PubMed

    Kim, Mikhail; Gais, Hans-Joachim

    2006-06-09

    A fully stereocontrolled synthesis of 3-oxacarbacyclin (3) and a formal synthesis of carbacyclin (2) are described. The syntheses are based on the conjugate addition-azoalkene-asymmetric olefination strategy. Its key features are (1) the stereoselective establishment of the complete omega-side chain of 2 and 3 through conjugate addition of the enantiopure C13-C20 alkenylcopper derivative 10 to the enantiopure C6-C12 bicyclic azoalkene 9 and (2) the 5E-stereoselective construction of the alpha-side chain through a Horner-Wadsworth-Emmons olefination of the bicyclic ketone 7 with the chiral lithium phosphonoacetate 26 with formation of ester E-27. The allylic alcohol 6 serves at late stage as the joint intermediate in the synthesis of 2 and 3.

  8. Increased functionality of methyl oleate using alkene metathesis

    USDA-ARS?s Scientific Manuscript database

    A series of alkene cross metathesis reactions were performed using a homogeneous ruthenium based catalyst. Using this technology, a variety of functional groups can be incorporated into the biobased starting material, methyl oleate. Trans-stilbene, styrene, methyl cinnamate and hexen-3-ol were all s...

  9. Recent advances in the development of alkyne metathesis catalysts

    PubMed Central

    Wu, Xian

    2011-01-01

    Summary The number of well-defined molybdenum and tungsten alkylidyne complexes that are able to catalyze alkyne metathesis reactions efficiently has been significantly expanded in recent years.The latest developments in this field featuring highly active imidazolin-2-iminato- and silanolate–alkylidyne complexes are outlined in this review. PMID:21286398

  10. Synthesis of cyclic sulfones by ring-closing metathesis.

    PubMed

    Yao, Qingwei

    2002-02-07

    A general and highly efficient synthesis of cyclic sulfones based on ring-closing metathesis has been developed. The synthetic utility of the resulting cyclic sulfones was demonstrated by their participation in stereoselective Diels-Alder reactions and transformation to cyclic dienes by the Ramberg-Bäcklund reaction.

  11. A Bicyclo[4.2.0]octene-Derived Monomer Provides Completely Linear Alternating Copolymers via Alternating Ring-Opening Metathesis Polymerization (AROMP).

    PubMed

    Tan, Li; Parker, Kathlyn A; Sampson, Nicole S

    2014-10-14

    Strained bicyclic carbomethoxy olefins were utilized as substrates in alternating ring-opening metathesis polymerization and found to provide low-dispersity polymers with novel backbones. The polymerization of methyl bicyclo[4.2.0]oct-7-ene-7-carboxylate with cyclohexene in the presence of the fast-initiating Grubbs catalyst (H2IMes)(3-Br-Pyr)2Cl2Ru=CHPh leads to a completely linear as well as alternating copolymer, as demonstrated by NMR spectroscopy, isotopic labeling, and gel permeation chromatography. In contrast, intramolecular chain-transfer reactions were observed with [5.2.0] and [3.2.0] bicyclic carbomethoxy olefins, although to a lesser extent than with the previously reported monocyclic cyclobutenecarboxylic ester monomers [Song A.; Parker K. A.; Sampson N. S.J. Am. Chem. Soc.2009, 131, 3444]. Inclusion of cyclohexyl rings fused to the copolymer backbone minimizes intramolecular chain-transfer reactions and provides a framework for creating alternating functionality in a one-step polymerization.

  12. Chiral benzamidinate ligands in rare-earth-metal coordination chemistry.

    PubMed

    Benndorf, Paul; Kratsch, Jochen; Hartenstein, Larissa; Preuss, Corinna M; Roesky, Peter W

    2012-11-05

    The treatment of the recently reported potassium salt (S)-N,N'-bis-(1-phenylethyl)benzamidinate ((S)-KPEBA) and its racemic isomer (rac-KPEBA) with anhydrous lanthanide trichlorides (Ln = Sm, Er, Yb, Lu) afforded mostly chiral complexes. The tris(amidinate) complex [{(S)-PEBA}(3)Sm], bis(amidinate) complexes [{Ln(PEBA)(2)(μ-Cl)}(2)] (Ln = Sm, Er, Yb, Lu), and mono(amidinate) compounds [Ln(PEBA)(Cl)(2)(thf)(n)] (Ln = Sm, Yb, Lu) were isolated and structurally characterized. As a result of steric effects, the homoleptic 3:1 complexes of the smaller lanthanide atoms Yb and Lu were not accessible. Furthermore, chiral bis(amidinate)-amido complexes [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were synthesized by an amine-elimination reaction and salt metathesis. All of these chiral bis- and tris(amidinate) complexes had additional axial chirality and they all crystallized as diastereomerically pure compounds. By using rac-PEBA as a ligand, an achiral meso arrangement of the ligands was observed. The catalytic activities and enantioselectivities of [{(S)-PEBA}(2)Ln{N(SiMe(3))(2)}] (Ln = Y, Lu) were investigated in hydroamination/cyclization reactions. A clear dependence of the rate of reaction and enantioselectivity on the ionic radius was observed, which showed higher reaction rates but poorer enantioselectivities for the yttrium compound.

  13. Chiral mirrors

    SciTech Connect

    Plum, Eric; Zheludev, Nikolay I.

    2015-06-01

    Mirrors are used in telescopes, microscopes, photo cameras, lasers, satellite dishes, and everywhere else, where redirection of electromagnetic radiation is required making them arguably the most important optical component. While conventional isotropic mirrors will reflect linear polarizations without change, the handedness of circularly polarized waves is reversed upon reflection. Here, we demonstrate a type of mirror reflecting one circular polarization without changing its handedness, while absorbing the other. The polarization-preserving mirror consists of a planar metasurface with a subwavelength pattern that cannot be superimposed with its mirror image without being lifted out of its plane, and a conventional mirror spaced by a fraction of the wavelength from the metasurface. Such mirrors enable circularly polarized lasers and Fabry-Pérot cavities with enhanced tunability, gyroscopic applications, polarization-sensitive detectors of electromagnetic waves, and can be used to enhance spectroscopies of chiral media.

  14. Synthesis of pterostilbene by Julie Olefination

    USDA-ARS?s Scientific Manuscript database

    A simple, stereoselective route for the synthesis of the biologically active compounds trans-pterostilbene and tetramethoxy stilbene from the readily available starting materials 3,5-dimethoxy benzyl alcohol and 4-hydroxy benzaldehyde was developed using Julia olefination as a key reaction....

  15. Olefin Recovery from Chemical Industry Waste Streams

    SciTech Connect

    A.R. Da Costa; R. Daniels; A. Jariwala; Z. He; A. Morisato; I. Pinnau; J.G. Wijmans

    2003-11-21

    The objective of this project was to develop a membrane process to separate olefins from paraffins in waste gas streams as an alternative to flaring or distillation. Flaring these streams wastes their chemical feedstock value; distillation is energy and capital cost intensive, particularly for small waste streams.

  16. Process feasibility of DME to olefin conversion

    SciTech Connect

    Tartamella, T.L.; Fullerton, K.L.; Lee, S.; Kulik, C.J.

    1994-12-31

    The production of hydrocarbons via a synthetic route has been extensively studied by Mobil through its methanol based Methanol-to-Gasoline (MTG) process. An alternative approach using dimethyl ether (DME) has been developed by the University of Akron -- UA/EPRI DME-to-Hydrocarbons Process. The process feasibility of the production of hydrocarbons from DME has been illustrated in a bench scale, fluidized bed reactor using ZSM-5 type catalyst. In an effort to satisfy the growing demand for olefins as an intermediate chemical feedstocks a mechanistic/kinetic study was developed. The synthesis of olefins has been studied in packed bed micro-reactor using ZSM-5 catalyst. Experimental work has given details of reaction kinetics and mechanism in the conversion of DME to olefins. DME concentration weight hourly space velocity (WHSV), as well as reactor temperature and pressure were investigated in the study. This work was used as a precursor to the production of olefins/hydrocarbons from DME in a fluidized bed reactor. Product gas analysis was performed using an external GC standard method.

  17. Polymerization Mechanism of α-Linear Olefin

    NASA Astrophysics Data System (ADS)

    Xing, Wen-guo; Zhang, Chang-qiao; Yu, Ping; Liu, Cheng-bu; Wei, Yun-he

    2010-02-01

    The density functional theory on the level of B3LYP/6-31G was empolyed to study the chain growth mechanism in polymerization process of α-linear olefin in TiCl3/AlEt2Cl catalytic system to synthesize drag reduction agent. Full parameter optimization without symmetry restrictions for reactants, products, the possible transition states, and intermediates was calculated. Vibration frequency was analyzed for all of stagnation points on the potential energy surface at the same theoretical level. The internal reaction coordinate was calculated from the transition states to reactants and products respectively. The results showed as follows: (i) Coordination compounds were formed on the optimum configuration of TiCl3/AlEt2Cl. (ii) The transition states were formed. The energy difference between transition states and the coordination compounds was 40.687 kJ/mol. (iii) Double bond opened and Ti-C(4) bond fractured, and the polymerization was completed. The calculation results also showed that the chain growth mechanism did not essentially change with the increase of carbon atom number of α-linear olefin. From the relationship between polymerization activation energy and carbon atom number of the α-linear olefin, it can be seen that the α-linear olefin monomers with 6-10 carbon atoms had low activation energy and wide range. It was optimum to synthesize drag reduction agent by polymerization.

  18. Bromination of olefins with HBr and DMSO.

    PubMed

    Karki, Megha; Magolan, Jakob

    2015-04-03

    A simple and inexpensive methodology is reported for the conversion of alkenes to 1,2-dibromo alkanes via oxidative bromination using HBr paired with dimethyl sulfoxide, which serves as the oxidant as well as cosolvent. The substrate scope includes 21 olefins brominated in good to excellent yields. Three of six styrene derivatives yielded bromohydrins under the reaction conditions.

  19. Light olefins from coal derived syngas

    SciTech Connect

    Sardesai, A.; Tartamella, T.; Lee, S.

    1996-12-31

    Synthesis of methanol from coal-derived synthesis gas is a well established technology, and methanol has been used as a feedstock for the synthesis of gasoline range hydrocarbons and olefins commercially. However, an efficient hydrocarbon synthesis process, based on a single-stage dimethyl ether synthesis from syngas, has been developed at the University of Akron. This UA/EPRI`s DTH (Dimethyl Ether to Hydrocarbons) process has significant advantages over its counterpart methanol conversion process in the areas of heat duties, hydrocarbon selectivities, product yield, and reactor size. Lower olefins are the intermediate products in the conversion of dimethyl ether to aromatic hydrocarbons. C{sub 2}-C{sub 4} olefins can be selectively produced by varying the operating parameters of the process, viz., temperature, pressure, DME concentration in the feed, space time, acidity of the catalyst, etc. The present work focuses on the effect of key process variables on the dimethyl ether conversion to lower olefins in a fixed bed microreactor system over ZSM-5 type zeolite catalyst. Experimental results with respect to gaseous hydrocarbon product yields and selectivities have been examined in this study.

  20. Understanding complex chiral plasmonics.

    PubMed

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-11-07

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the 'host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.

  1. Lewis acid promoted titanium alkylidene formation: off-cycle intermediates relevant to olefin trimerization catalysis.

    PubMed

    Sattler, Aaron; VanderVelde, David G; Labinger, Jay A; Bercaw, John E

    2014-07-30

    Two new precatalysts for ethylene and α-olefin trimerization, (FI)Ti(CH2SiMe3)2Me and (FI)Ti(CH2CMe3)2Me (FI = phenoxy-imine), have been synthesized and structurally characterized by X-ray diffraction. (FI)Ti(CH2SiMe3)2Me can be activated with 1 equiv of B(C6F5)3 at room temperature to give the solvent-separated ion pair [(FI)Ti(CH2SiMe3)2][MeB(C6F5)3], which catalytically trimerizes ethylene or 1-pentene to produce 1-hexene or C15 olefins, respectively. The neopentyl analogue (FI)Ti(CH2CMe3)2Me is unstable toward activation with B(C6F5)3 at room temperature, giving no discernible diamagnetic titanium complexes, but at -30 °C the following can be observed by NMR spectroscopy: (i) formation of the bis-neopentyl cation [(FI)Ti(CH2CMe3)2](+), (ii) α-elimination of neopentane to give the neopentylidene complex [(FI)Ti(═CHCMe3)](+), and (iii) subsequent conversion to the imido-olefin complex [(MeOAr2N═)Ti(OArHC═CHCMe3)](+) via an intramolecular metathesis reaction with the imine fragment of the (FI) ligand. If the reaction is carried out at low temperature in the presence of ethylene, catalytic production of 1-hexene is observed, in addition to the titanacyclobutane complex [(FI)Ti(CH(CMe3)CH2CH2)](+), resulting from addition of ethylene to the neopentylidene [(FI)Ti(═CHCMe3)](+). None of the complexes observed spectroscopically subsequent to [(FI)Ti(CH2CMe3)2](+) is an intermediate or precursor for ethylene trimerization, but notwithstanding these off-cycle pathways, [(FI)Ti(CH2CMe3)2](+) is a precatalyst that undergoes rapid initiation to generate a catalyst for trimerizing ethylene or 1-pentene.

  2. One step formation of propene from ethene or ethanol through metathesis on nickel ion-loaded silica.

    PubMed

    Iwamoto, Masakazu

    2011-09-13

    Increased propene production is presently one of the most significant objectives in petroleum chemistry. Especially the one-step conversion of ethene to propene (ETP reaction, 3C₂H₄ →2C₃H₆) is the most desired process. In our efforts, nickel ion-loaded mesoporous silica could turn a new type of ETP reaction into reality. The one-step conversion of ethene was 68% and the propene selectivity was 48% in a continuous gas-flow system at 673 K and atmospheric pressure. The reactivity of lower olefins and the dependences of the ETP reaction on the contact time and the partial pressure of ethene were consistent with a reaction mechanism involving dimerization of ethene to 1-butene, isomerization of 1-butene to 2-butene, and metathesis of 2-butene and ethene to yield propene. The reaction was then expanded to an ethanol-to-propene reaction on the same catalyst, in which two possible reaction routes are suggested to form ethene from ethanol. The catalysts were characterized mainly by EXAFS and TPR techniques. The local structures of the nickel species active for the ETP reaction were very similar to that of layered nickel silicate, while those on the inert catalysts were the same as that of NiO particles.

  3. Sequential one-pot combination of multireactions through multicatalysis: a general approach to rapid assembly of functionalized push-pull olefins, phenols, and 2-methyl-2H-chromenes.

    PubMed

    Ramachary, Dhevalapally B; Ramakumar, Kinthada; Bharanishashank, Adluri; Narayana, Vidadala V

    2010-11-08

    A general, sustainable and practical process for the sequential cascade one-pot synthesis of library of highly substituted push-pull olefins, phenols and 2-methyl-2H-chromenes was reported through multicatalysis cascade (MCC) reactions. Direct sequential one-pot combination of amine- or amino acid-catalyzed cascade Knoevenagel/Michael/aldol condensation/decarboxylation with other reactions like amine- or amino acid-catalyzed cascade Claisen-Schmidt/iso-aromatization, Claisen-Schmidt/isomerization, Claisen-Schmidt/iso-aromatization/isomerization, Michael addition, Claisen-Schmidt/Michael, ruthenium-base-silica-catalyzed ring closing metathesis/base-induced ring-opening/benzylic oxidation/[1,7]-sigmatropic hydrogen shift, or ruthenium-base-heat-catalyzed ring closing metathesis/base-induced ring-opening/[1,7]-sigmatropic hydrogen shift reactions of alkyl acetoacetates, a variety of aldehydes and alkyl halides furnished the highly functionalized push-pull olefins, phenols and 2-methyl-2H-chromenes with high yields. The yields and regioselectivities were good to excellent. Evidence for a new reaction pathway involving in situ formation of novel push-pull dienamines under amine- or amino acid-catalysis is presented along with examples demonstrating the amenability of the process to MCC chemistry.

  4. Chiral organoborane Lewis pairs derived from pyridylferrocene.

    PubMed

    Chen, Jiawei; Lalancette, Roger A; Jäkle, Frieder

    2014-07-14

    In an effort to develop a new class of redox-active chiral Lewis pairs, pyridine and borane moieties with different steric and electronic properties were introduced onto a planar chiral 1,2-disubstituted ferrocene framework. Metathesis of lithiated, stannylated, or mercuriated pyridylferrocenes with boron halides afforded (pR)-2-[bis(pentafluorophenyl)boryl]-1-(3,5-dimethylpyrid-2-yl)ferrocene (4-Pf), (pR)-2-[dimesitylboryl]-1-(3,5-dimethylpyrid-2-yl)ferrocene (4-Mes), (pS)-2-(bis(pentafluorophenyl)boryl)-1-(2-trimethylsilylpyrid-6-yl)ferrocene (5-Pf), or (pS)-2-[dimesitylboryl]-1-(2-trimethylsilylpyrid-6-yl)ferrocene (5-Mes). The borylated products were analyzed by multinuclear NMR spectroscopy, HRMS, and single-crystal X-ray diffraction. Chiral HPLC and optical-rotation measurements were employed to assess the stereoselectivity of the borylation process and to establish the correct stereochemical assignments. The strength of the B-N interactions were investigated in solution and in the solid state. Compounds 4-Pf and 4-Mes formed robust 'closed' B-N heterocyclic systems that proved to be perfectly stable to air and moisture, whereas 5-Pf established a dynamic equilibrium, in which the B-N heterocycle was observed exclusively at room temperature, but opened up at high temperature according to (19)F NMR exchange spectroscopy data. As a consequence, 5-Pf reacted readily with a molecule of water to generate a ring-opened pyridinium borate. The combination of bulky borane and bulky pyridyl groups in 5-Mes led to a completely 'open' frustrated Lewis pair system with uncomplexed pyridine and borane groups, even at room temperature. Electrochemical studies were performed and the effect of preparative ferrocene oxidation on the structural features was also explored.

  5. Chiral gravitational waves from chiral fermions

    NASA Astrophysics Data System (ADS)

    Anber, Mohamed M.; Sabancilar, Eray

    2017-07-01

    We report on a new mechanism that leads to the generation of primordial chiral gravitational waves, and hence, the violation of the parity symmetry in the Universe. We show that nonperturbative production of fermions with a definite helicity is accompanied by the generation of chiral gravitational waves. This is a generic and model-independent phenomenon that can occur during inflation, reheating and radiation eras, and can leave imprints in the cosmic microwave background polarization and may be observed in future ground- and space-based interferometers. We also discuss a specific model where chiral gravitational waves are generated via the production of light chiral fermions during pseudoscalar inflation.

  6. Computational study of productive and non-productive cycles in fluoroalkene metathesis.

    PubMed

    Rybáčková, Markéta; Hošek, Jan; Šimůnek, Ondřej; Kolaříková, Viola; Kvíčala, Jaroslav

    2015-01-01

    A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda-Grubbs 2(nd) generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the calculations showed that the cross-metathesis of perfluoro- or perhaloalkenes should be a feasible process and that the metathesis is not very sensitive to stereochemical issues.

  7. Computational study of productive and non-productive cycles in fluoroalkene metathesis

    PubMed Central

    Rybáčková, Markéta; Hošek, Jan; Šimůnek, Ondřej; Kolaříková, Viola

    2015-01-01

    Summary A detailed DFT study of the mechanism of metathesis of fluoroethene, 1-fluoroethene, 1,1-difluoroethene, cis- and trans-1,2-difluoroethene, tetrafluoroethene and chlorotrifluoroethene catalysed with the Hoveyda–Grubbs 2nd generation catalyst was performed. It revealed that a successful metathesis of hydrofluoroethenes is hampered by a high preference for a non-productive catalytic cycle proceeding through a ruthenacyclobutane intermediate bearing fluorines in positions 2 and 4. Moreover, the calculations showed that the cross-metathesis of perfluoro- or perhaloalkenes should be a feasible process and that the metathesis is not very sensitive to stereochemical issues. PMID:26664636

  8. Rational design of cyclopropane-based chiral PHOX ligands for intermolecular asymmetric Heck reaction

    PubMed Central

    Rubina, Marina; Sherrill, William M; Barkov, Alexey Yu

    2014-01-01

    Summary A novel class of chiral phosphanyl-oxazoline (PHOX) ligands with a conformationally rigid cyclopropyl backbone was synthesized and tested in the intermolecular asymmetric Heck reaction. Mechanistic modelling and crystallographic studies were used to predict the optimal ligand structure and helped to design a very efficient and highly selective catalytic system. Employment of the optimized ligands in the asymmetric arylation of cyclic olefins allowed for achieving high enantioselectivities and significantly suppressing product isomerization. Factors affecting the selectivity and the rate of the isomerization were identified. It was shown that the nature of this isomerization is different from that demonstrated previously using chiral diphosphine ligands. PMID:25161709

  9. Chirality of Viral Capsids

    NASA Astrophysics Data System (ADS)

    Dharmavaram, Sanjay; Xie, Fangming; Bruinsma, Robijn; Klug, William; Rudnick, Joseph

    Most icosahedral viruses are classified by their T-number which identifies their capsid in terms of the number of capsomers and their relative arrangement. Certain T-numbers (T = 7 for instance) are inherently chiral (with no reflection planes) while others (e.g. T = 1) are achiral. We present a Landau-Brazovskii (LB) theory for weak crystallization in which a scalar order parameter that measures density of capsid proteins successfully predicts the various observed T-numbers and their respective chiralities. We find that chiral capsids gain stability by spontaneously breaking symmetry from an unstable chiral state. The inherently achiral LB-free energy does not preferentially select a particular chiral state from its mirror reflection. Based on the physical observation that proteins are inherently chiral molecules with directional interactions, we propose a new chiral term to the LB energy as a possible selection mechanism for chirality.

  10. The effect of aliphatic olefins on the stability of diesel fuel

    SciTech Connect

    Adiwar; Batts, B.D.

    1995-04-01

    The effect of aliphatic olefins on the storage stability of a number of distillates was observed and characterized, mainly by determining the amounts of total insolubles formed during accelerated ageing. It was observed that the aliphatic olefins, in light cycle oil (LCO), a product of catalytic cracking, accelerated the degradation process in accordance with general expectations and in straight run diesel (SRD) and hydrotreated diesel (HTD), aliphatic olefins were shown to have no effect on stability. However, contrary to expectations, the aliphatic olefins inhibited the degradation process of light waxy gas oil (LWGO). The effect of aliphatic isomers on the degradation of LCO is in the order of terminal olefins < internal olefins < branched chain olefins. The effect of aliphatic olefinic isomers on LWGO is, on the other hand, in the order of terminal olefin > internal olefins > branched chain olefins. Three possible mechanisms to explain the effect of aliphatic olefins on the LCO and LWGO samples are proposed.

  11. Chiral Inorganic Nanostructures.

    PubMed

    Ma, Wei; Xu, Liguang; de Moura, André F; Wu, Xiaoling; Kuang, Hua; Xu, Chuanlai; Kotov, Nicholas A

    2017-06-28

    The field of chiral inorganic nanostructures is rapidly expanding. It started from the observation of strong circular dichroism during the synthesis of individual nanoparticles (NPs) and their assemblies and expanded to sophisticated synthetic protocols involving nanostructures from metals, semiconductors, ceramics, and nanocarbons. Besides the well-established chirality transfer from bioorganic molecules, other methods to impart handedness to nanoscale matter specific to inorganic materials were discovered, including three-dimentional lithography, multiphoton chirality transfer, polarization effects in nanoscale assemblies, and others. Multiple chiral geometries were observed with characteristic scales from ångströms to microns. Uniquely high values of chiral anisotropy factors that spurred the development of the field and differentiate it from chiral structures studied before, are now well understood; they originate from strong resonances of incident electromagnetic waves with plasmonic and excitonic states typical for metals and semiconductors. At the same time, distinct similarities with chiral supramolecular and biological systems also emerged. They can be seen in the synthesis and separation methods, chemical properties of individual NPs, geometries of the nanoparticle assemblies, and interactions with biological membranes. Their analysis can help us understand in greater depth the role of chiral asymmetry in nature inclusive of both earth and space. Consideration of both differences and similarities between chiral inorganic, organic, and biological nanostructures will also accelerate the development of technologies based on chiroplasmonic and chiroexcitonic effects. This review will cover both experiment and theory of chiral nanostructures starting with the origin and multiple components of mirror asymmetry of individual NPs and their assemblies. We shall consider four different types of chirality in nanostructures and related physical, chemical, and

  12. Introduction to chiral symmetry

    SciTech Connect

    Koch, V.

    1996-01-08

    These lectures are an attempt to a pedagogical introduction into the elementary concepts of chiral symmetry in nuclear physics. Effective chiral models such as the linear and nonlinear sigma model will be discussed as well as the essential ideas of chiral perturbation theory. Some applications to the physics of ultrarelativistic heavy ion collisions will be presented.

  13. A chameleon catalyst for nonheme iron-promoted olefin oxidation.

    PubMed

    Iyer, Shyam R; Javadi, Maedeh Moshref; Feng, Yan; Hyun, Min Young; Oloo, Williamson N; Kim, Cheal; Que, Lawrence

    2014-11-18

    We report the chameleonic reactivity of two nonheme iron catalysts for olefin oxidation with H2O2 that switch from nearly exclusive cis-dihydroxylation of electron-poor olefins to the exclusive epoxidation of electron-rich olefins upon addition of acetic acid. This switching suggests a common precursor to the nucleophilic oxidant proposed to Fe(III)-η(2)-OOH and electrophilic oxidant proposed to Fe(V)(O)(OAc), and reversible coordination of acetic acid as a switching pathway.

  14. Self-Assembly of Disorazole C1 through a One-Pot Alkyne Metathesis Homodimerization Strategy**

    PubMed Central

    Ralston, Kevin J; Ramstadius, H Clinton; Brewster, Richard C; Niblock, Helen S; Hulme, Alison N

    2015-01-01

    Alkyne metathesis is increasingly explored as a reliable method to close macrocyclic rings, but there are no prior examples of an alkyne-metathesis-based homodimerization approach to natural products. In this approach to the cytotoxic C2-symmetric marine-derived bis(lactone) disorazole C1, a highly convergent, modular strategy is employed featuring cyclization through an ambitious one-pot alkyne cross-metathesis/ring-closing metathesis self-assembly process. PMID:25926364

  15. Conversion of olefins to liquid motor fuels

    DOEpatents

    Rabo, Jule A.; Coughlin, Peter K.

    1988-01-01

    Linear and/or branched claim C.sub.2 to C.sub.12 olefins are converted to hydrocarbon mixtures suitable for use as liquid motor fuels by contact with a catalyst capable of ensuring the production of desirable products with only a relatively minor amount of heavy products boiling beyond the diesel oil range. The catalyst having desirable stability during continuous production operations, comprises a steam stabilized zeolite Y catalyst of hydrophobic character, desirably in aluminum-extracted form. The olefins such as propylene, may be diluted with inerts, such as paraffins or with water, the latter serving to moderate the acidity of the catalyst, or to further moderate the activity of the aluminum-extracted catalyst, so as to increase the effective life of the catalyst.

  16. Heterobimetallic s-block hydrides by σ-bond metathesis.

    PubMed

    Liptrot, David J; Hill, Michael S; Mahon, Mary F

    2014-08-04

    Reactions between PhSiH3 and alkali-metal diamidoalkylmagnesiates ([M{N(SiMe3)2}2MgBu], M = Li, Na, K) provide either selective alkyl metathesis or the formation of polyhydride aggregates contingent upon the identity of the Group 1 metal. In the case of [M{N(SiMe3)2}2MgBu], this reactivity results in a structurally unprecedented dodecametallic decahydride cluster species.

  17. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, Michael S.; Saunders, Randall

    1997-01-01

    Coupling agents based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization.

  18. Photochemical preparation of olefin addition catalysts

    NASA Technical Reports Server (NTRS)

    Gray, Harry B. (Inventor); Rembaum, Alan (Inventor); Gupta, Amitava (Inventor)

    1978-01-01

    Novel polymer supported catalysts are prepared by photo-irradiation of low valent transition metal compounds such as Co.sub.2 (CO).sub.8, Rh.sub.4 (CO).sub.12 or Ru.sub.3 (CO).sub.12 in the presence of solid polymers containing amine ligands such as polyvinyl pyridine. Hydroformylation of olefins to aldehydes at ambient conditions has been demonstrated.

  19. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    PubMed

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-03-08

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines were evaluated.

  20. Baryons and chiral symmetry

    NASA Astrophysics Data System (ADS)

    Liu, Keh-Fei

    The relevance of chiral symmetry in baryons is highlighted in three examples in the nucleon spectroscopy and structure. The first one is the importance of chiral dynamics in understanding the Roper resonance. The second one is the role of chiral symmetry in the lattice calculation of πNσ term and strangeness. The third one is the role of chiral U(1) anomaly in the anomalous Ward identity in evaluating the quark spin and the quark orbital angular momentum. Finally, the chiral effective theory for baryons is discussed.

  1. Reduction in Syllable Onsets in the Acquisition of Polish: Deletion, Coalescence, Metathesis and Gemination

    ERIC Educational Resources Information Center

    Lukaszewicz, Beata

    2007-01-01

    This paper focuses on four strategies of onset reduction employed by a single child (4;0-4;4) acquiring Polish: deletion, coalescence, metathesis, and gemination. Deletion and coalescence occur in word-initial onsets while metathesis and gemination are restricted to word-medial position. The data, which constitute an intriguing "conspiracy" case…

  2. Reduction in Syllable Onsets in the Acquisition of Polish: Deletion, Coalescence, Metathesis and Gemination

    ERIC Educational Resources Information Center

    Lukaszewicz, Beata

    2007-01-01

    This paper focuses on four strategies of onset reduction employed by a single child (4;0-4;4) acquiring Polish: deletion, coalescence, metathesis, and gemination. Deletion and coalescence occur in word-initial onsets while metathesis and gemination are restricted to word-medial position. The data, which constitute an intriguing "conspiracy" case…

  3. Chiral symmetry and chiral-symmetry breaking

    SciTech Connect

    Peskin, M.E.

    1982-12-01

    These lectures concern the dynamics of fermions in strong interaction with gauge fields. Systems of fermions coupled by gauge forces have a very rich structure of global symmetries, which are called chiral symmetries. These lectures will focus on the realization of chiral symmetries and the causes and consequences of thier spontaneous breaking. A brief introduction to the basic formalism and concepts of chiral symmetry breaking is given, then some explicit calculations of chiral symmetry breaking in gauge theories are given, treating first parity-invariant and then chiral models. These calculations are meant to be illustrative rather than accurate; they make use of unjustified mathematical approximations which serve to make the physics more clear. Some formal constraints on chiral symmetry breaking are discussed which illuminate and extend the results of our more explicit analysis. Finally, a brief review of the phenomenological theory of chiral symmetry breaking is presented, and some applications of this theory to problems in weak-interaction physics are discussed. (WHK)

  4. Understanding complex chiral plasmonics

    NASA Astrophysics Data System (ADS)

    Duan, Xiaoyang; Yue, Song; Liu, Na

    2015-10-01

    Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant and simple analytical model, which can describe, predict, and comprehend the chiroptical spectra in detail. Our study will shed light on designing well-controlled chiral-achiral coupling platforms for reliable chiral sensing.Chiral nanoplasmonics exhibits great potential for novel nanooptical devices due to the generation of a strong chiroptical response within nanoscale metallic structures. Recently, a number of different approaches have been utilized to create chiral nanoplasmonic structures. However, particularly for tailoring nanooptical chiral sensing devices, the understanding of the resulting chiroptical response when coupling chiral and achiral structures together is crucial and has not been completely understood to date. Here, we present a thorough and step-by-step experimental study to understand the intriguing chiral-achiral coupling scheme. We set up a hybrid plasmonic system, which bears resemblance to the `host-guest' system in supramolecular chemistry to analyze and explain the complex chiral response both at the chiral and achiral plasmonic resonances. We also provide an elegant

  5. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    SciTech Connect

    Rathke, J.W.; Klingler, R.J.

    1992-12-31

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  6. Supported organometallic catalysts for hydrogenation and Olefin Polymerization

    DOEpatents

    Marks, Tobin J.; Ahn, Hongsang

    2001-01-01

    Novel heterogeneous catalysts for the which hydrogenation of olefins and arenes with high conversion rates under ambient conditions and the polymerization of olefins have been developed. The catalysts are synthesized from Ziegler-type precatalysts by supporting them on sulfate-modified zirconia.

  7. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    DOEpatents

    Rathke, Jerome W.; Klingler, Robert J.

    1993-01-01

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  8. Cobalt carbonyl catalyzed olefin hydroformylation in supercritical carbon dioxide

    DOEpatents

    Rathke, J.W.; Klingler, R.J.

    1993-03-30

    A method of olefin hydroformylation is provided wherein an olefin reacts with a carbonyl catalyst and with reaction gases such as hydrogen and carbon monoxide in the presence of a supercritical reaction solvent, such as carbon dioxide. The invention provides higher yields of n-isomer product without the gas-liquid mixing rate limitation seen in conventional Oxo processes using liquid media.

  9. Gelation induced supramolecular chirality: chirality transfer, amplification and application.

    PubMed

    Duan, Pengfei; Cao, Hai; Zhang, Li; Liu, Minghua

    2014-08-14

    Supramolecular chirality defines chirality at the supramolecular level, and is generated from the spatial arrangement of component molecules assembling through non-covalent interactions such as hydrogen bonding, van der Waals interactions, π-π stacking, hydrophobic interactions and so on. During the formation of low molecular weight gels (LMWGs), one kind of fascinating soft material, one frequently encounters the phenomenon of chirality as well as chiral nanostructures, either from chiral gelators or even achiral gelators. A view of gelation-induced supramolecular chirality will be very helpful to understand the self-assembly process of the gelator molecules as well as the chiral structures, the regulation of the chirality in the gels and the development of the "smart" chiral materials such as chiroptical devices, catalysts and chiral sensors. It necessitates fundamental understanding of chirality transfer and amplification in these supramolecular systems. In this review, recent progress in gelation-induced supramolecular chirality is discussed.

  10. Practical carbon–carbon bond formation from olefins through nickel-catalyzed reductive olefin hydrocarbonation

    PubMed Central

    Lu, Xi; Xiao, Bin; Zhang, Zhenqi; Gong, Tianjun; Su, Wei; Yi, Jun; Fu, Yao; Liu, Lei

    2016-01-01

    New carbon–carbon bond formation reactions expand our horizon of retrosynthetic analysis for the synthesis of complex organic molecules. Although many methods are now available for the formation of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds via transition metal-catalyzed cross-coupling of alkyl organometallic reagents, direct use of readily available olefins in a formal fashion of hydrocarbonation to make C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds remains to be developed. Here we report the discovery of a general process for the intermolecular reductive coupling of unactivated olefins with alkyl or aryl electrophiles under the promotion of a simple nickel catalyst system. This new reaction presents a conceptually unique and practical strategy for the construction of C(sp2)–C(sp3) and C(sp3)–C(sp3) bonds without using any organometallic reagent. The reductive olefin hydrocarbonation also exhibits excellent compatibility with varieties of synthetically important functional groups and therefore, provides a straightforward approach for modification of complex organic molecules containing olefin groups. PMID:27033405

  11. Alkaline Earth-Olefin Complexes with Secondary Interactions.

    PubMed

    Roşca, Sorin-Claudiu; Dinoi, Chiara; Caytan, Elsa; Dorcet, Vincent; Etienne, Michel; Carpentier, Jean-François; Sarazin, Yann

    2016-05-04

    Strontium and calcium (alkaline earth: Ae) olefin complexes stabilised by secondary Ae⋅⋅⋅F-C and β-agostic Ae⋅⋅⋅H-Si interactions are presented. Olefin coordination onto the alkaline earths is plain in the solid state, and it is thermodynamically favoured over the coordination of THF. The existence of the Ae⋅⋅⋅olefin interactions is corroborated by solution NMR data and DFT computations. The coordination mode of the olefin varies with steric effects and, if enforced, olefin dissociation can be compensated by the other non-covalent interactions, as supported by DFT computations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Homologation of olefins by methanol over ZSM-5 zeolite

    SciTech Connect

    Behrsing, T.; Mole, T.; Smart, P.; Western, R.J.

    1986-11-01

    /sup 13/C-Labeled methanol has been coreacted with excess C/sub 6/ olefins (2-methylpentene-1 or hexene-1) over the proton form of ZSM-5 zeolite under such conditions (ca. 550 K and a 2-s contact time) so that the C/sub 6/ olefins undergo extensive reaction while the methanol undergoes partial conversion to hydrocarbons. The resulting mixture of olefins was then hydrogenated to facilitate isotopic analysis. The /sup 13/C label was most abundant in the C/sub 7/ products, consistent with the hypothesis that the methanol is converted mainly by the homologation of an olefin to form an olefin with one more methylene group. 13 references.

  13. Enantioselective total synthesis of clavirolide C. Applications of Cu-catalyzed asymmetric conjugate additions and Ru-catalyzed ring-closing metathesis.

    PubMed

    Brown, M Kevin; Hoveyda, Amir H

    2008-10-01

    The first enantioselective total synthesis of clavirolide C, a member of the dolabellane family of diterpenes isolated from Pacific soft coral Clavularia viridis, is disclosed. The total synthesis features the application of chiral amino acid based ligands in Cu-catalyzed asymmetric conjugate addition (ACA) reactions and a relatively rare application of catalytic ring-closing metathesis to access an 11-membered ring structure. The total synthesis effort has spawned the development of a new protocol for NHC.Cu-catalyzed ACA of alkylaluminum reagents to beta-substituted cycloalkenones. The enantioselective clavirolide C synthesis requires 17 steps (longest linear sequence), affords the target molecule in 3.5% overall yield, and confirms the stereochemical assignment for the natural product.

  14. Enantioselective Total Synthesis of Clavirolide C. Applications of Cu-Catalyzed Asymmetric Conjugate Additions and Ru-Catalyzed Ring-Closing Metathesis

    PubMed Central

    Brown, M. Kevin

    2009-01-01

    The first enantioselective total synthesis of clavirolide C, a member of the dolabellane family of diterpenes isolated from Pacific soft coral Clavularia viridis, is disclosed. The total synthesis features the application of chiral amino acid-based ligands in Cu-catalyzed asymmetric conjugate addition (ACA) reactions and a relatively rare application of catalytic ring-closing metathesis to access an eleven-membered ring structure. The total synthesis effort has spawned the development of a new protocol for NHC∙Cu-catalyzed ACA of alkylaluminum reagents to β-substituted cycloalkenones. The enantioselective clavirolide C synthesis requires seventeen steps (longest linear sequence), affords the target molecule in 3.5% overall yield, and confirms the stereochemical assignment for the natural product. PMID:18778057

  15. Total Synthesis of the Antitumor Antibiotic (±)-Streptonigrin: First- and Second-Generation Routes for de Novo Pyridine Formation Using Ring-Closing Metathesis

    PubMed Central

    2013-01-01

    The total synthesis of (±)-streptonigrin, a potent tetracyclic aminoquinoline-5,8-dione antitumor antibiotic that reached phase II clinical trials in the 1970s, is described. Two routes to construct a key pentasubstituted pyridine fragment are depicted, both relying on ring-closing metathesis but differing in the substitution and complexity of the precursor to cyclization. Both routes are short and high yielding, with the second-generation approach ultimately furnishing (±)-streptonigrin in 14 linear steps and 11% overall yield from inexpensive ethyl glyoxalate. This synthesis will allow for the design and creation of druglike late-stage natural product analogues to address pharmacological limitations. Furthermore, assessment of a number of chiral ligands in a challenging asymmetric Suzuki–Miyaura cross-coupling reaction has enabled enantioenriched (up to 42% ee) synthetic streptonigrin intermediates to be prepared for the first time. PMID:24328139

  16. Ir-catalyzed allylic amination/ring-closing metathesis: a new route to enantioselective synthesis of cyclic beta-amino alcohol derivatives.

    PubMed

    Lee, Jun Hee; Shin, Seunghoon; Kang, Jahyo; Lee, Sang-gi

    2007-09-14

    Ir-catalyzed allylic aminations of (E)-4-benzyloxy-2-butenyl methyl carbonate with benzylamine using Feringa's (Sa,Sc,Sc)-phosphoramidite as a chiral ligand afforded linear-aminated achiral product N,O-dibenzyl-4-amino-2-buten-1-ol regioselectively (linear/branched = >99/1), whereas the (E)-5-benzyloxy-2-pentenyl methyl carbonate showed completely opposite regioselectivity (linear/branched = >1/99) and afforded the optically active (3R)-N,O-dibenzylated 3-amino-1-penten-5-ol with very high enantioselectivity (96% ee), which was used as a key intermediate for the effective synthesis of various cyclic beta-amino alcohol derivatives through ring-closing metathesis in high yields.

  17. Chiral rotational spectroscopy

    NASA Astrophysics Data System (ADS)

    Cameron, Robert P.; Götte, Jörg B.; Barnett, Stephen M.

    2016-09-01

    We introduce chiral rotational spectroscopy, a technique that enables the determination of the orientated optical activity pseudotensor components BX X, BY Y, and BZ Z of chiral molecules, in a manner that reveals the enantiomeric constitution of a sample and provides an incisive signal even for a racemate. Chiral rotational spectroscopy could find particular use in the analysis of molecules that are chiral solely by virtue of their isotopic constitution and molecules with multiple chiral centers. A basic design for a chiral rotational spectrometer together with a model of its functionality is given. Our proposed technique offers the more familiar polarizability components αX X, αY Y, and αZ Z as by-products, which could see it find use even for achiral molecules.

  18. Emerging chirality in nanoscience.

    PubMed

    Wang, Yong; Xu, Jun; Wang, Yawen; Chen, Hongyu

    2013-04-07

    Chirality in nanoscience may offer new opportunities for applications beyond the traditional fields of chirality, such as the asymmetric catalysts in the molecular world and the chiral propellers in the macroscopic world. In the last two decades, there has been an amazing array of chiral nanostructures reported in the literature. This review aims to explore and categorize the common mechanisms underlying these systems. We start by analyzing the origin of chirality in simple systems such as the helical spring and hair vortex. Then, the chiral nanostructures in the literature were categorized according to their material composition and underlying mechanism. Special attention is paid to highlight systems with original discoveries, exceptional structural characteristics, or unique mechanisms.

  19. Chiral fluctuations in achiral systems

    NASA Astrophysics Data System (ADS)

    Harris, Robert A.

    2001-12-01

    "Chiral fluctuations" are defined, and their relation to "dynamic chirality" is discussed. Simple experiments to measure chiral fluctuations are proposed. The unique aspects of these measurements for systems such as atomic clusters and gases are outlined.

  20. Process for reacting alcohols and olefins

    SciTech Connect

    Miller, J.T.; Nevitt, T.D.

    1985-01-29

    A method for producing branched aliphatic hydrocarbons by reacting H/sub 2/ with a C/sub 1/-C/sub 6/ alcohol and/or a C/sub 2/-C/sub 6/ olefin in the presence of a cadmium component and a support which comprises an amorphous refractory inorganic oxide, a pillared smectite or vermiculite clay, a molecular sieve consisting essentially of unexchanged or cation-exchanged chabazite, clinoptilite, zeolite A, zeolite L, zeolite X, zeolite Y, ultrastable zeolite Y, or crystalline borosilicate molecular sieve, or a combination thereof.

  1. Fluidized bed pyrolysis to gases containing olefins

    SciTech Connect

    Kuester, J.L.

    1980-01-01

    Recent gasification data are presented for a system designed to produce liquid hydrocarbon fuel from various biomass feedstocks. The factors under investigation were feedstock type, fluidizing gas type, residence time, temperature and catalyst usage. The response was gas phase composition. A fluidized bed system was utilized with a separate regenerator-combustor. An olefin content as high as 39 mole % was achieved. Hydrogen/carbon monoxide ratios were easily manipulated via steam addition over a broad range with an autocatalytic effect apparent for most feedstocks.

  2. Syntheses of Synthetic Hydrocarbons Via Alpha Olefins.

    DTIC Science & Technology

    1981-10-01

    Chem. Educ., 42, 502 (1965). 4. A. Priola, C. Corna , and S. Cesca, Macromolecules, 13, 1110 (1980). 5. R. F . Brown, Organic Chemistry, Wadsworth...AD-A110 380 GULF RESEARCH AND DEVELOPENT Co PITTSBURGH PA F /G T/A 1 SYNTHESES OF SYNTHETIC HYDROCARBONS VIA ALPHA OLEFINS.(U) OCT 81 B L CUPPLES, A...FOR THE COMMANDER F . D. CHERRY, Chief Nonmetallic Materials Division "If your address has changed, if you wish to be removed from our mailing list

  3. Periodic chiral structures

    NASA Technical Reports Server (NTRS)

    Jaggard, Dwight L.; Engheta, Nader; Pelet, Philippe; Liu, John C.; Kowarz, Marek W.; Kim, Yunjin

    1989-01-01

    The electromagnetic properties of a structure that is both chiral and periodic are investigated using coupled-mode equations. The periodicity is described by a sinusoidal perturbation of the permittivity, permeability, and chiral admittance. The coupled-mode equations are derived from physical considerations and used to examine bandgap structure and reflected and transmitted fields. Chirality is observed predominantly in transmission, whereas periodicity is present in both reflection and transmission.

  4. Planar plasmonic chiral nanostructures

    NASA Astrophysics Data System (ADS)

    Zu, Shuai; Bao, Yanjun; Fang, Zheyu

    2016-02-01

    A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response.A strong chiral optical response induced at a plasmonic Fano resonance in a planar Au heptamer nanostructure was experimentally and theoretically demonstrated. The scattering spectra show the characteristic narrow-band feature of Fano resonances for both left and right circular polarized lights, with a chiral response reaching 30% at the Fano resonance. Specifically, we systematically investigate the chiral response of planar heptamers with gradually changing the inter-particle rotation angles and separation distance. The chiral spectral characteristics clearly depend on the strength of Fano resonances and the associated near-field optical distributions. Finite element method simulations together with a multipole expansion method demonstrate that the enhanced chirality is caused by the excitation of magnetic quadrupolar and electric toroidal dipolar modes. Our work provides an effective method for the design of 2D nanostructures with a strong chiral response. Electronic supplementary information (ESI) available

  5. Highly E-Selective and Enantioselective Michael Addition to Electron-Deficient Internal Alkynes Under Chiral Iminophosphorane Catalysis.

    PubMed

    Uraguchi, Daisuke; Yamada, Kohei; Ooi, Takashi

    2015-08-17

    A highly E-selective and enantioselective conjugate addition of 2-benzyloxythiazol-5(4H)-ones to β-substituted alkynyl N-acyl pyrazoles is achieved under the catalysis of a P-spiro chiral iminophosphorane. Simultaneous control of the newly generated central chirality and olefin geometry is possible with a wide array of the alkynyl Michael acceptors possessing different aromatic and aliphatic β-substituents, as well as the various α-amino acid-derived thiazolone nucleophiles. This protocol provides access to structurally diverse, optically active α-amino acids bearing a geometrically defined trisubstituted olefinic component at the α-position. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Characterizing optical chirality

    SciTech Connect

    Bliokh, Konstantin Y.; Nori, Franco

    2011-02-15

    We examine the recently introduced measure of chirality of a monochromatic optical field [Y. Tang and A. E. Cohen, Phys. Rev. Lett. 104, 163901 (2010)] using the momentum (plane-wave) representation and helicity basis. Our analysis clarifies the physical meaning of the measure of chirality and unveils its close relation to the polarization helicity, spin angular momentum, energy density, and Poynting energy flow. We derive the operators of the optical chirality and of the corresponding chiral momentum, which acquire remarkably simple forms in the helicity representation.

  7. Chiral atomically thin films.

    PubMed

    Kim, Cheol-Joo; Sánchez-Castillo, A; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm(-1)) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  8. Chiral atomically thin films

    NASA Astrophysics Data System (ADS)

    Kim, Cheol-Joo; Sánchez-Castillo, A.; Ziegler, Zack; Ogawa, Yui; Noguez, Cecilia; Park, Jiwoong

    2016-06-01

    Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm-1) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.

  9. Block copolymer adhesion promoters via ring-opening metathesis polymerization

    DOEpatents

    Kent, M.S.; Saunders, R.

    1997-02-18

    Coupling agents are disclosed based on functionalized block copolymers for bonding thermoset polymers to solid materials. These are polymers which possess at least two types of functional groups, one which is able to attach to and react with solid surfaces, and another which can react with a thermoset resin, which are incorporated as pendant groups in monomers distributed in blocks (typically two) along the backbone of the chain. The block copolymers in this invention are synthesized by living ring-opening metathesis polymerization. 18 figs.

  10. Synthetic chemistry with fullerenes. Photooxygenation of olefins

    SciTech Connect

    Tokuyama, Hidetoshi; Nakamura, Eiichi

    1994-03-11

    Under irradiation with visible or UV (>290 nm) light in the presence of molecular oxygen and a minute amount of fullerenes, olefins and dienes undergo ene and Diels-Alder reactions with singlet oxygen to give photooxygenation products. The regio-and stereoselectives of the photooxygenation of {beta}-myrcene, (+)-pulegone, 4-methylpent-3-en-2-ol, and (+)-limonene were very similiar to those observed in known singlet oxygen reactions, indicating that the fullerene-sensitized reaction generates free singlet oxygen. The efficiency of fullerenes and conventional sensitizers was qualitively examined by using the Diels-Alder reaction between {sup 1}O{sub 2} and furan-2-carboxylic acid as a probe. Among those examined, C{sub 70} was found to be the most effective. The reaction was the fastest and completed with as little as 0.0001 equiv of C{sub 70}. C{sub 60} and hematoporphyrin were found to be of similiar efficiency. The methanofullerene 13, which lacks one olefinic conjunction in the C{sub 60} core, was as good as C{sub 60} itself, but the aminofullerene 14, lacking six double bonds, was quite inferior. The fullerene carboxylic acid 15, which was previously shown to show considerable biochemical activity, was found to be capable of generating singlet oxygen in aqueous DMSO. 25 refs., 1 tab.

  11. Methods for the synthesis of olefins and derivatives

    DOEpatents

    Burk, Mark J; Pharkya, Priti; Van Dien, Stephen J; Burgard, Anthony P; Schilling, Christophe H

    2013-06-04

    The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

  12. Methods for the synthesis of olefins and derivatives

    DOEpatents

    Burk, Mark J.; Pharkya, Priti; Van Dien, Stephen J.; Burgard, Anthony P.; Schilling, Christophe H.

    2011-09-27

    The invention provides a method of producing acrylic acid. The method includes contacting fumaric acid with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylic acid per mole of fumaric acid. Also provided is an acrylate ester. The method includes contacting fumarate diester with a sufficient amount of ethylene in the presence of a cross-metathesis transformation catalyst to produce about two moles of acrylate ester per mole of fumarate diester. An integrated process for process for producing acrylic acid or acrylate ester is provided which couples bioproduction of fumaric acid with metathesis transformation. An acrylic acid and an acrylate ester production also is provided.

  13. Z-Selective Ruthenium Metathesis Catalysts: Comparison of Nitrate and Nitrite X-type Ligands

    PubMed Central

    Pribisko, Melanie A.; Ahmed, Tonia S.; Grubbs, Robert H.

    2014-01-01

    Two new Ru-based metathesis catalysts, 3 and 4, have been synthesized for the purpose of comparing their catalytic properties to those of their cis-selective nitrate analogues, 1 and 2. Although catalysts 3 and 4 exhibited slower initiation rates than 1 and 2, they maintained high cis-selectivity in homodimerization and ring-opening metathesis polymerization reactions. Furthermore, the nitrite catalysts displayed higher cis-selectivity than 2 for ring-opening metathesis polymerizations, and 4 delivered higher yields of polymer. PMID:25484484

  14. Chiral magnetic superconductivity

    NASA Astrophysics Data System (ADS)

    Kharzeev, Dmitri E.

    2017-03-01

    Materials with charged chiral quasiparticles in external parallel electric and magnetic fields can support an electric current that grows linearly in time, corresponding to diverging DC conductivity. From experimental viewpoint, this "Chiral Magnetic Superconductivity" (CMS) is thus analogous to conventional superconductivity. However the underlying physics is entirely different - the CMS does not require a condensate of Cooper pairs breaking the gauge degeneracy, and is thus not accompanied by Meissner effect. Instead, it owes its existence to the (temperature-independent) quantum chiral anomaly and the conservation of chirality. As a result, this phenomenon can be expected to survive to much higher temperatures. Even though the chirality of quasiparticles is not strictly conserved in real materials, the chiral magnetic superconductivity should still exhibit itself in AC measurements at frequencies larger than the chirality-flipping rate, and in microstructures of Dirac and Weyl semimetals with thickness below the mean chirality-flipping length that is about 1 - 100 μm. In nuclear physics, the CMS should contribute to the charge-dependent elliptic flow in heavy ion collisions.

  15. Superenantioselective chiral surface explosions.

    PubMed

    Gellman, Andrew J; Huang, Ye; Feng, Xu; Pushkarev, Vladimir V; Holsclaw, Brian; Mhatre, Bharat S

    2013-12-26

    Chiral inorganic materials predated life on Earth, and their enantiospecific surface chemistry may have played a role in the origins of biomolecular homochirality. However, enantiospecific differences in the interaction energies of chiral molecules with chiral surfaces are small and typically lead to modest enantioselectivities in adsorption, catalysis, and chemistry on chiral surfaces. To yield high enantioselectivities, small energy differences must be amplified by reaction mechanisms such as autocatalytic surface explosions which have nonlinear kinetics. Herein, we report the first observations of superenantiospecificity resulting from an autocatalytic surface explosion reaction of a chiral molecule on a naturally chiral surface. R,R- and S,S-tartaric acid decompose via a vacancy-mediated surface explosion mechanism on Cu single crystal surfaces. When coupled with surface chirality, this leads to decomposition rates that exhibit extraordinarily high enantiospecificity. On the enantiomorphs of naturally chiral Cu(643)(R&S), Cu(17,5,1)(R&S), Cu(531)(R&S) and Cu(651)(R&S) single crystal surfaces, R,R- and S,S-tartaric acid exhibit enantiospecific decomposition rates that differ by as much as 2 orders of magnitude, despite the fact that the effective rates constants for decomposition differ by less than a factor of 2.

  16. Synthesis of nanosized silicon particles by a rapid metathesis reaction

    SciTech Connect

    Won, C.W.; Nersisyan, H.H.; Won, H.I.; Lee, H.H.

    2009-11-15

    A solid-state rapid metathesis reaction was performed in a bed of sodium silicofluoride (Na{sub 2}SiF{sub 6}) and sodium azide (NaN{sub 3}) powders diluted with sodium fluoride (NaF), to produce silicon nanoparticles. After a local ignition of Na{sub 2}SiF{sub 6}+4NaN{sub 3}+kNaF mixture (here k is mole number of NaF), the reaction proceeded in a self-sustaining combustion mode developing high temperatures (950-1000 deg. C) on very short time scales (a few seconds). Silicon nanoparticles prepared by the combustion process was easily separated from the salt byproducts by simple washing with distilled water. The structural and morphological studies on the nanoparticles were carried out using X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM). The mean size of silicon particles calculated from the FESEM image was about 37.75 nm. FESEM analysis also shows that the final purified product contains a noticeable amount of silicon fibers, dendrites and blocks, along with nanoparticles. The mechanism of Si nanostructures formation is discussed and a simple model for interpretation of experimental results is proposed. - Graphical abstract: Silicon nanoparticles 37.75 nm in mean diameter was obtained by rapid metathesis reaction performed in Na{sub 2}SiF{sub 6}+4NaN{sub 3} powder bed diluted with NaF.

  17. Splitting a C-O bond in dialkylethers with bis(1,2,4-tri-t-butylcyclopentadienyl) cerium-hydride does not occur by a sigma-bond metathesis pathway: a combined experimental and DFT computational study

    SciTech Connect

    Werkema, Evan; Yahia, Ahmed; Maron, Laurent; Eisenstein, Odile; Andersen, Richard

    2010-04-06

    Addition of diethylether to [1,2,4(Me3C)3C5H2]2CeH, abbreviated Cp'2CeH, gives Cp'2CeOEt and ethane. Similarly, di-n-propyl- or di-n-butylether gives Cp'2Ce(O-n-Pr) and propane or Cp'2Ce(O-n-Bu) and butane, respectively. Using Cp'2CeD, the propane and butane contain deuterium predominantly in their methyl groups. Mechanisms, formulated on the basis of DFT computational studies, show that the reactions begin by an alpha or beta-CH activation with comparable activation barriers but only the beta-CH activation intermediate evolves into the alkoxide product and an olefin. The olefin then inserts into the Ce-H bond forming the alkyl derivative, Cp'2CeR, that eliminates alkane. The alpha-CH activation intermediate is in equilibrium with the starting reagents, Cp'2CeH and the ether, which accounts for the deuterium label in the methyl groups of the alkane. The one-step sigma-bond metathesis mechanism has a much higher activation barrier than either of the two-step mechanisms.

  18. Molecular model for chirality phenomena.

    PubMed

    Latinwo, Folarin; Stillinger, Frank H; Debenedetti, Pablo G

    2016-10-21

    Chirality is a hallmark feature for molecular recognition in biology and chemical physics. We present a three-dimensional continuum model for studying chirality phenomena in condensed phases using molecular simulations. Our model system is based upon a simple four-site molecule and incorporates non-trivial kinetic behavior, including the ability to switch chirality or racemize, as well as thermodynamics arising from an energetic preference for specific chiral interactions. In particular, we introduce a chiral renormalization parameter that can locally favor either homochiral or heterochiral configurations. Using this model, we explore a range of chirality-specific phenomena, including the kinetics of chiral inversion, the mechanism of spontaneous chiral symmetry breaking in the liquid, chirally driven liquid-liquid phase separation, and chiral crystal structures.

  19. Selective Oxidation and Ammoxidation of Olefins by Heterogeneous Catalysis.

    ERIC Educational Resources Information Center

    Grasselli, Robert K.

    1986-01-01

    Shows how the ammoxidation of olefins can be understood in terms of free radicals and surface bound organometallic intermediates. Also illustrates the close intellectual relationships between heterogeneous catalysis and organometallic chemistry. (JN)

  20. Direct observation of OH production from the ozonolysis of olefins

    NASA Astrophysics Data System (ADS)

    Donahue, Neil M.; Kroll, Jesse H.; Anderson, James G.; Demerjian, Kenneth L.

    Ozone olefin reactions may be a significant source of OH in the urban atmosphere, but current evidence for OH production is indirect and contested. We report the first direct observation of OH radicals from the reaction of ozone with a series of olefins (ethene, isoprene, trans-2-butene and 2,3 dimethyl-2-butene) in 4-6 torr of nitrogen. Using LIF to directly observe the steady-state of OH produced by the initial ozone-olefin reaction and subsequently destroyed by the OH-olefin reaction, we are able to establish OH yields broadly consistent with indirect values. The identification of the OH is unequivocal, and there is no indication that it is produced by a secondary process. To support these observations, we present a complete ab-initio potential energy surface for the O3-ethene reaction, extending from the reactants to available products.

  1. Selective Oxidation and Ammoxidation of Olefins by Heterogeneous Catalysis.

    ERIC Educational Resources Information Center

    Grasselli, Robert K.

    1986-01-01

    Shows how the ammoxidation of olefins can be understood in terms of free radicals and surface bound organometallic intermediates. Also illustrates the close intellectual relationships between heterogeneous catalysis and organometallic chemistry. (JN)

  2. Direct catalytic conversion of synthesis gas to lower olefins

    SciTech Connect

    Janardanarao, M. )

    1990-09-01

    Direct conversion of synthesis gas to lower olefins has been considered as a possible solution to meet the growing demand for chemical feedstocks such as ethylene, propylene, and butylenes. This review covers the various catalyst systems and operating conditions that have been used in meeting this objective. Though the product distribution in Fischer--Tropsch synthesis is governed by the existence of an Anderson--Schultz--Flory polymerization model, certain modifications in the catalyst formulations have produced a shift toward lower molecular weight olefins. At the present time, the yields and selectivities of lower olefins are far from optimal, but continued research efforts in this area may lead to the development of stable catalyst systems capable of producing highly desirable distributions of lower olefins.

  3. Unsupported catalysts in the production of olefins

    SciTech Connect

    Kreuter, W.; Wernicke, H.

    1980-07-01

    A description is given of a process for the production of olefins in two stages wherein, in the first stage, a heavy petroleum fraction is hydrogenated essentially in the liquid phase in the presence of hydrogen and a hydrogenation catalyst and, in the second stage, the thus-hydrogenated fraction is subjected to thermal cracking in the vapor phase in the presence of steam, the improvement which comprises employing as the hydrogenation catalyst a support-free catalyst consisting essentially of at least one of Co-Mo, Ni-Mo, Co-Mo sulfide, Ni-Co-Mo sulfide, Ni-Mo sulfide, Ni-Co sulfide, Co-mo oxide, Ni-Co-Mo oxide, Ni-Mo oxide, Ni-Co oxide, Ni-W sulfide, Ni-W oxide, or organometallic complexes of aforementioned metallic mixtures.

  4. Selective conversion of syngas to light olefins.

    PubMed

    Jiao, Feng; Li, Jinjing; Pan, Xiulian; Xiao, Jianping; Li, Haobo; Ma, Hao; Wei, Mingming; Pan, Yang; Zhou, Zhongyue; Li, Mingrun; Miao, Shu; Li, Jian; Zhu, Yifeng; Xiao, Dong; He, Ting; Yang, Junhao; Qi, Fei; Fu, Qiang; Bao, Xinhe

    2016-03-04

    Although considerable progress has been made in direct synthesis gas (syngas) conversion to light olefins (C2(=)-C4(=)) via Fischer-Tropsch synthesis (FTS), the wide product distribution remains a challenge, with a theoretical limit of only 58% for C2-C4 hydrocarbons. We present a process that reaches C2(=)-C4(=) selectivity as high as 80% and C2-C4 94% at carbon monoxide (CO) conversion of 17%. This is enabled by a bifunctional catalyst affording two types of active sites with complementary properties. The partially reduced oxide surface (ZnCrO(x)) activates CO and H2, and C-C coupling is subsequently manipulated within the confined acidic pores of zeolites. No obvious deactivation is observed within 110 hours. Furthermore, this composite catalyst and the process may allow use of coal- and biomass-derived syngas with a low H2/CO ratio.

  5. Olefins and chemical regulation in Europe: REACH.

    PubMed

    Penman, Mike; Banton, Marcy; Erler, Steffen; Moore, Nigel; Semmler, Klaus

    2015-11-05

    REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) is the European Union's chemical regulation for the management of risk to human health and the environment (European Chemicals Agency, 2006). This regulation entered into force in June 2007 and required manufacturers and importers to register substances produced in annual quantities of 1000 tonnes or more by December 2010, with further deadlines for lower tonnages in 2013 and 2018. Depending on the type of registration, required information included the substance's identification, the hazards of the substance, the potential exposure arising from the manufacture or import, the identified uses of the substance, and the operational conditions and risk management measures applied or recommended to downstream users. Among the content developed to support this information were Derived No-Effect Levels or Derived Minimal Effect Levels (DNELs/DMELs) for human health hazard assessment, Predicted No Effect Concentrations (PNECs) for environmental hazard assessment, and exposure scenarios for exposure and risk assessment. Once registered, substances may undergo evaluation by the European Chemicals Agency (ECHA) or Member State authorities and be subject to requests for additional information or testing as well as additional risk reduction measures. To manage the REACH registration and related activities for the European olefins and aromatics industry, the Lower Olefins and Aromatics REACH Consortium was formed in 2008 with administrative and technical support provided by Penman Consulting. A total of 135 substances are managed by this group including 26 individual chemical registrations (e.g. benzene, 1,3-butadiene) and 13 categories consisting of 5-26 substances. This presentation will describe the content of selected registrations prepared for 2010 in addition to the significant post-2010 activities. Beyond REACH, content of the registrations may also be relevant to other European activities, for

  6. Catalyst control in sequential asymmetric allylic substitution: stereodivergent access to N,N-diprotected unnatural amino acids.

    PubMed

    Tosatti, Paolo; Campbell, Amanda J; House, David; Nelson, Adam; Marsden, Stephen P

    2011-07-01

    The sequential use of Cu-catalyzed asymmetric allylic alkylation, olefin cross-metathesis, and Ir-catalyzed asymmetric allylic amination allows the concise, stereodivergent synthesis of complex chiral amines with complete regiocontrol and good diastereoselectivity, exemplified by the synthesis of a pair of diastereoisomeric unnatural branched amino acid derivatives.

  7. Applications of chiral symmetry

    SciTech Connect

    Pisarski, R.D.

    1995-03-01

    The author discusses several topics in the applications of chiral symmetry at nonzero temperature. First, where does the rho go? The answer: up. The restoration of chiral symmetry at a temperature T{sub {chi}} implies that the {rho} and a{sub 1} vector mesons are degenerate in mass. In a gauged linear sigma model the {rho} mass increases with temperature, m{sub {rho}}(T{sub {chi}}) > m{sub {rho}}(0). The author conjectures that at T{sub {chi}} the thermal {rho} - a{sub 1}, peak is relatively high, at about {approximately}1 GeV, with a width approximately that at zero temperature (up to standard kinematic factors). The {omega} meson also increases in mass, nearly degenerate with the {rho}, but its width grows dramatically with temperature, increasing to at least {approximately}100 MeV by T{sub {chi}}. The author also stresses how utterly remarkable the principle of vector meson dominance is, when viewed from the modern perspective of the renormalization group. Secondly, he discusses the possible appearance of disoriented chiral condensates from {open_quotes}quenched{close_quotes} heavy ion collisions. It appears difficult to obtain large domains of disoriented chiral condensates in the standard two flavor model. This leads to the last topic, which is the phase diagram for QCD with three flavors, and its proximity to the chiral critical point. QCD may be very near this chiral critical point, and one might thereby generated large domains of disoriented chiral condensates.

  8. Kinetics and mechanism of olefin catalytic hydroalumination by organoaluminum compounds

    NASA Astrophysics Data System (ADS)

    Koledina, K. F.; Gubaidullin, I. M.

    2016-05-01

    The complex reaction mechanism of α-olefin catalytic hydroalumination by alkylalanes is investigated via mathematical modeling that involves plotting the kinetic models for the individual reactions that make up a complex system and a separate study of their principles. Kinetic parameters of olefin catalytic hydroalumination are estimated. Activation energies of the possible steps of the schemes of complex reaction mechanisms are compared and possible reaction pathways are determined.

  9. Zwitterionic Group VIII transition metal initiators supported by olefin ligands

    SciTech Connect

    Bazan, Guillermo C; Chen, Yaofeng

    2011-10-25

    A zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that catalyzes the formation of polypropylene and high molecular weight polyethylene. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct. The present invention also provides methods of polymerizing olefin monomers using zwitterionic catalysts, particularly polypropylene and high molecular weight polyethylene.

  10. Self‐Assembly of Disorazole C1 through a One‐Pot Alkyne Metathesis Homodimerization Strategy†

    PubMed Central

    Ralston, Kevin J.; Ramstadius, H. Clinton; Brewster, Richard C.; Niblock, Helen S.

    2015-01-01

    Abstract Alkyne metathesis is increasingly explored as a reliable method to close macrocyclic rings, but there are no prior examples of an alkyne‐metathesis‐based homodimerization approach to natural products. In this approach to the cytotoxic C2‐symmetric marine‐derived bis(lactone) disorazole C1, a highly convergent, modular strategy is employed featuring cyclization through an ambitious one‐pot alkyne cross‐metathesis/ring‐closing metathesis self‐assembly process. PMID:27346897

  11. Stereodivergent Olefination of Enantioenriched Boronic Esters

    PubMed Central

    Armstrong, Roly J.; García‐Ruiz, Cristina; Myers, Eddie L.

    2016-01-01

    Abstract A stereodivergent coupling reaction between vinyl halides and boronic esters is described. This coupling process proceeds without a transition‐metal catalyst, instead proceeding by electrophilic selenation or iodination of a vinyl boronate complex followed by stereospecific syn or anti elimination. Chiral, nonracemic boronic esters could be coupled with complete enantiospecificity. The process enables the highly stereoselective synthesis of either the E or Z alkene from a single isomer of a vinyl coupling partner. PMID:27958668

  12. Catalysis of dynamical chiral symmetry breaking by chiral chemical potential

    NASA Astrophysics Data System (ADS)

    Braguta, V. V.; Kotov, A. Yu.

    2016-05-01

    In this paper, we study the properties of media with chiral imbalance parametrized by chiral chemical potential. It is shown that depending on the strength of interaction between constituents in the media the chiral chemical potential either creates or enhances dynamical chiral symmetry breaking. Thus, the chiral chemical potential plays the role of the catalyst of dynamical chiral symmetry breaking. Physically, this effect results from the appearance of the Fermi surface and additional fermion states on this surface, which take part in dynamical chiral symmetry breaking. An interesting conclusion which can be drawn is that at sufficiently small temperature chiral plasma is unstable with respect to condensation of Cooper pairs and dynamical chiral symmetry breaking even for vanishingly small interactions between constituents.

  13. Chirality Differentiation by Diffusion in Chiral Nematic Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Jiang, Jinghua; Yang, Deng-Ke

    2017-01-01

    Chirality is of great importance in the living world. It helps differentiate biochemical reactions such as those that take place during digestion. It may also help differentiate physical processes such as diffusion. Aiming to study the latter effect, we investigate the diffusion of guest chiral molecules in chiral nematic (cholesteric) liquid-crystal hosts. We discover that the diffusion dramatically depends on the handedness of the guest and host molecules and the chiral differentiation is greatly enhanced by the proper alignment of the liquid-crystal host. The diffusion of a guest chiral molecule in a chiral host with the same handedness is much faster than in a chiral host with opposite handedness. We also observe that the differentiation of chirality depends on the diffusion direction with respect to the twisting direction (helical axis). These results might be important in understanding effects of chirality on physical processes that take place in biological organisms. In addition, this effect could be utilized for enantiomer separation.

  14. Acidic polysaccharide mimics via ring-opening metathesis polymerization.

    PubMed

    Wathier, Michel; Stoddart, Stephanie S; Sheehy, Matthew J; Grinstaff, Mark W

    2010-11-17

    An efficient and general synthetic strategy for the preparation of high-molecular-weight hydrophilic polymers bearing both carboxylic acid and hydroxyl pendant groups is described. Specifically, poly(5,6-dihydroxyoxanorbornane carboxylic acid) with molecular weight ranging from ∼100 000 to 5 000 000 g/mol was prepared by ring-opening metathesis polymerization of methyl 5-oxanorbornene-2-carboxylate in the presence of Grubbs catalyst II and subsequently modified to tune the hydrophobic/hydrophilic properties by the introduction of either hydroxyl or carboxylic acid functionalities. These polymers mimic the natural acidic polysaccharide alginate and form hydrogels with polylysine. These polymers belong to a class of carbohydrate-like polymers, which are of interest for investigating the relationships between chemical structure and rheological properties as well as for providing new synthetic polysaccharide substitutes for applications in the biotechnology and pharmaceutical industries.

  15. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis.

    PubMed

    Röttger, Max; Domenech, Trystan; van der Weegen, Rob; Breuillac, Antoine; Nicolaÿ, Renaud; Leibler, Ludwik

    2017-04-07

    Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

  16. High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis

    NASA Astrophysics Data System (ADS)

    Röttger, Max; Domenech, Trystan; van der Weegen, Rob; Breuillac, Antoine; Nicolaÿ, Renaud; Leibler, Ludwik

    2017-04-01

    Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

  17. Spintronics: Chiral damping

    PubMed Central

    Kim, Kyoung-Whan; Lee, Hyun-Woo

    2016-01-01

    The analysis of the magnetic domain wall motion in a nanostructured magnetic system with strong spin-orbit coupling shows that the energy dissipation can be chiral when the inversion symmetry is broken. PMID:26906956

  18. Chiral magnetic wave

    SciTech Connect

    Kharzeev, Dmitri E.; Yee, Ho-Ung

    2011-04-15

    We consider a relativistic plasma containing charged chiral fermions in an external magnetic field, e.g. a chirally symmetric quark-gluon plasma created in relativistic heavy ion collisions. We show that triangle anomalies imply the existence of a new type of collective gapless excitation in this system that stems from the coupling between the density waves of the electric and chiral charges; we call it ''the chiral magnetic wave'' (CMW). The CMW exists even in a neutral plasma, i.e. in the absence of the axial and vector chemical potentials. We demonstrate the existence of CMW and study its properties using three different approaches: i) relativistic magnetohydrodynamics; ii) dimensional reduction to (1+1) Sine-Gordon model, appropriate in a strong magnetic field; and iii) holographic QCD (Sakai-Sugimoto model), appropriate at strong coupling. We also briefly discuss the phenomenological implications of the CMW for heavy ion collisions.

  19. Relativistic Chiral Kinetic Theory

    NASA Astrophysics Data System (ADS)

    Stephanov, Mikhail

    2016-12-01

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi:10.1103/PhysRevLett.113.182302; J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: 10.1103/PhysRevLett.115.021601; M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: 10.1103/PhysRevLett.116.122302].

  20. Chiral Hypervalent, Pentacoordinated Phosphoranes.

    PubMed

    Krasowska, Dorota; Chrzanowski, Jacek; Kiełbasiński, Piotr; Drabowicz, Józef

    2016-11-21

    This review presents synthetic procedures applied to the preparation of chiral (mainly optically active) pentacoordinated, hypervalent mono and bicyclic phosphoranes. The mechanisms of their stereoisomerization and their selected interconversions are also presented.

  1. Biocatalysis: Chiral cascades

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Bo; Reetz, Manfred T.

    2015-12-01

    Racemic or enantiomerically pure alcohols can be converted with high yield into enantiopure chiral amines in a one-pot redox-neutral cascade process by the clever combination of an alcohol dehydrogenase and an appropriate amine dehydrogenase.

  2. Chirality and protein biosynthesis.

    PubMed

    Banik, Sindrila Dutta; Nandi, Nilashis

    2013-01-01

    Chirality is present at all levels of structural hierarchy of protein and plays a significant role in protein biosynthesis. The macromolecules involved in protein biosynthesis such as aminoacyl tRNA synthetase and ribosome have chiral subunits. Despite the omnipresence of chirality in the biosynthetic pathway, its origin, role in current pathway, and importance is far from understood. In this review we first present an introduction to biochirality and its relevance to protein biosynthesis. Major propositions about the prebiotic origin of biomolecules are presented with particular reference to proteins and nucleic acids. The problem of the origin of homochirality is unresolved at present. The chiral discrimination by enzymes involved in protein synthesis is essential for keeping the life process going. However, questions remained pertaining to the mechanism of chiral discrimination and concomitant retention of biochirality. We discuss the experimental evidence which shows that it is virtually impossible to incorporate D-amino acids in protein structures in present biosynthetic pathways via any of the two major steps of protein synthesis, namely aminoacylation and peptide bond formation reactions. Molecular level explanations of the stringent chiral specificity in each step are extended based on computational analysis. A detailed account of the current state of understanding of the mechanism of chiral discrimination during aminoacylation in the active site of aminoacyl tRNA synthetase and peptide bond formation in ribosomal peptidyl transferase center is presented. Finally, it is pointed out that the understanding of the mechanism of retention of enantiopurity has implications in developing novel enzyme mimetic systems and biocatalysts and might be useful in chiral drug design.

  3. The quest for chirality

    SciTech Connect

    Bonner, W.A.

    1996-07-01

    The indispensable role played by homochirality and chiral homogeneity in the self-replication of crucial biomolecules is stressed, with the conclusion that life could neither exist nor originate without these chiral molecular attributes. Hypotheses historically proposed for the origin of chiral molecules on Earth are reviewed, including biogenic theories as well as abiotic theories embracing both indeterminate and determinate mechanisms. Indeterminate mechanisms, including autocatalytic symmetry breaking, asymmetric adsorption on quartz and clay minerals, and asymmetric syntheses in chiral crystals, are discussed and evaluated in the context of the prebiotic environment. Abiotic determinate mechanisms based on electric, magnetic and gravitational fields, on circularly polarized light (CPL), and on parity violation effects are summarized, with the emphasis that only CPL has proved practicable experimentally, but that it would be implausible on the primitive Earth. Mechanisms for the amplification of small, indigenous enantiomeric excesses are discussed, with one involving the partial polymerization of amino acids and the partial hydrolysis of polypeptides suggested as potentially viable prebiotically. Aspects of the turbulent, chirality-destructive primeval environment are described, with the conclusion that all of the above mechanisms for the {ital terrestrial} prebiotic origin of chirality would be non-viable, and that an alternative extraterrestrial source for the accumulation of chiral molecules on primitive Earth must have been operative. A scenario for this is outlined, in which we postulate that asymmetric photolysis of the organic mantles on interstellar grains in molecular clouds by circularly polarized ultraviolet synchrotron radiation from the neutron star remnants of supernovae produces chiral molecules in the grain mantles. (Abstract Truncated)

  4. Electrodynamics of chiral matter

    NASA Astrophysics Data System (ADS)

    Qiu, Zebin; Cao, Gaoqing; Huang, Xu-Guang

    2017-02-01

    Many-body systems with chiral fermions can exhibit novel transport phenomena that violate parity and time-reversal symmetries, such as the chiral magnetic effect, the anomalous Hall effect, and the anomalous generation of charge. Based on the Maxwell-Chern-Simons electrodynamics, we examine some electromagnetic and optical properties of such systems including the electrostatics, the magnetostatics, the propagation of electromagnetic waves, the novel optical effects, etc.

  5. Development of optically transparent cyclic olefin photoresist binder resins

    NASA Astrophysics Data System (ADS)

    Rhodes, Larry F.; Chang, Chun; Burns, Cheryl; Barnes, Dennis A.; Bennett, Brian; Seger, Larry; Wu, Xiaoming; Sobek, Andy; Mishak, Mike; Peterson, Craig; Langsdorf, Leah; Hada, Hideo; Shimizu, Hiroaki; Sasaki, Kazuhito

    2005-05-01

    Of all candidate 193 nm photoresist binder resins, transition metal catalyzed vinyl addition cyclic olefin (i.e., norbornene) polymers (PCO) hold the promise of high transparency and excellent etch resistance. In order to access lower molecular weight polymers, which are typically used in photoresists, α-olefin chain transfer agents (CTAs) are used in synthesizing vinyl addition poly(norbornenes). For example, HFANB (α,α-bis(trifluoromethyl)bicyclo [2.2.1]hept-5-ene-2-ethanol) homopolymers (p(HFANB)) with molecular weights (Mn) less than 5000 have been synthesized using such chain transfer agents. However, the optical density (OD) at 193 nm of these materials was found to rise as their molecular weights decreased consistent with a polymer end group effect. Extensive NMR and MS analysis of these polymers revealed that olefinic end groups derived from the chain transfer agent were responsible for the deleterious rise in OD. Chemical modification of these end groups by epoxidation, hydrogenation, hydrosilation, etc. lowers the OD of the polymer by removing the olefinic chromophore, however, it does require a second synthetic step. Thus a new class of non-olefinic chain transfer agents has been developed at Promerus that allow for excellent control of vinyl addition cyclic olefin polymer molecular weight and low optical density without the need of a post-polymerization chemical modification. Low molecular weight homopolymers of HFANB have been synthesized using these chain transfer agents that exhibit ODs <= 0.07 absorbance units per micron. This molecular weight control technology has been applied to both positive tone and negative tone vinyl addition cyclic olefin binder resins. Lithographic and etch performance of positive tone photoresists based on these binder resins will be presented.

  6. Chiral nihility effects on energy flow in chiral materials.

    PubMed

    Qiu, Cheng-Wei; Burokur, Nawaz; Zouhd, Saïd; Li, Le-Wei

    2008-01-01

    The propagation of electromagnetic plane waves in an isotropic chiral medium is characterized, and a special interest is shown in chiral nihility and the effects of chirality on energy transmission. In particular, the wave impedance is matched to that of free space. Moreover, the refractive index n is also matched in impedance to that of free space when an appropriate value of the chirality is chosen. A "chiral nihility" medium is explored in which both the permittivity and the permeability tend to zero. Some specific case studies of chiral nihility are presented, and Brewster angles are found to cover an extremely wide range. The E-field distributions in these different cases where the chiral slab is placed in free space are analyzed by using the appropriate constitutive relations. It is shown from numerical calculations that one can obtain some critical characteristics of the effects of chirality on energy transmission and reflection, such as transparency and power tunneling.

  7. Enantioselective synthesis of chiral sulfinates using chiral diamines.

    PubMed

    Nakamura, Shuichi; Tateyama, Motoaki; Sugimoto, Hideki; Nakagawa, Masaya; Watanabe, Yoshihiko; Shibata, Norio; Toru, Takeshi

    2005-02-01

    The reaction of p-toluenesulfinyl chloride with alcohols in the presence of chiral diamines was examined. Chiral sulfinates were obtained in good yields with enantioselectivity up to 76% ee. Copyright 2005 Wiley-Liss, Inc.

  8. Chiral biphenyl diphosphines for asymmetric catalysis: stereoelectronic design and industrial perspectives.

    PubMed

    Jeulin, Séverine; de Paule, Sébastien Duprat; Ratovelomanana-Vidal, Virginie; Genêt, Jean-Pierre; Champion, Nicolas; Dellis, Philippe

    2004-04-20

    Two original chiral diphosphines, SYNPHOS and DIFLUORPHOS, have been synthesized on multigram scales. Their steric and electronic profiles have been established in comparison with the commonly used 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl and 6,6'-dimethoxy-2,2'-bis(diphenylphosphino)-1,1'-biphenyl ligands. A screening study of the four ligands in Ru(II)-catalyzed asymmetric hydrogenation of prochiral ketones and olefins has been performed. It revealed that the stereoelectronic features of the ligand and the substrate deeply influenced the enantioselectivities obtained in asymmetric hydrogenation, SYNPHOS and DIFLUORPHOS being fully complementary in terms of enantioselectivity for this reaction.

  9. Catalytic Asymmetric Nazarov Cyclization of Heteroaryl Vinyl Ketones through a Crystallographically Defined Chiral Dinuclear Nickel Complex.

    PubMed

    Takeda, Takuya; Harada, Shinji; Nishida, Atsushi

    2015-11-06

    A Ni(NTf2)2 and tetradentate bisimino-bisquinoline ligand complex catalyzed the enantioselective Nazarov cyclization of heteroaryl vinyl ketones. An X-ray-quality crystal was obtained from a mixture of the Ni complex and the substrate, which was the dinuclear chiral Ni complex. From information regarding the structure of the complex, the substrate was distorted to form a helical shape, and the carbon atoms involved in bond formation were close to each other. In addition, mechanistic studies revealed that the configuration of the olefin moiety was isomerized before bond formation.

  10. Chirality of light and its interaction with chiral matter

    NASA Astrophysics Data System (ADS)

    Tang, Yiqiao

    This thesis conducts a systematic study on the chirality of light and its interaction with chiral matter. In the theory section, we introduce a measure of local density of chirality, applying to arbitrary electromagnetic fields. This optical chirality suggests the existence of superchiral modes, which are more selective than circularly polarized light (CPL) in preferentially exciting single enantiomers in certain regions of space. Experimentally, we demonstrate an 11-fold enhancement over CPL in discriminating chiral fluorophores of single handedness in a precisely sculpted superchiral field. This result agrees to within 15% with theoretical predictions. Any chiral configuration of point charges is beyond the scope of our theory on optical chirality. To address chiroptical excitations at nanoscale, we develop a model of twisted dipolar oscillators. We design a simple tunable chiral nanostructure and observe localized chiroptical "hot spots" with dramatically enhanced circular differential scattering. Our work on superchiral light and 3D chiral metamaterials establishes optical chirality as a fundamental and tunable property of light, with implications ranging from plasmonic sensors, absolute asymmetric synthesis to new strategies for fabricating three-dimensional chiral metamaterials. This thesis is organized as such: Chapter 1 provides a background on previous studies of chiroptical phenomena, and recent efforts in preparing chiral metamaterials. Chapter 2 derives theory on optical chirality, superchiral modes and coupled-dipolar oscillators at nanoscale. Chapter 3 introduces material, apparatus, and pitfalls in chiroptical experiments. Chapter 4 is an overview of the experimental procedure and results on generating and observing superchiral enhancement. Chapter 5 describes the experiments on using spectroscopic polarization microscopy to study chiral 3D chiral metamaterials. Finally in Chapter 6, I discuss quantization of optical chirality and perspectives on

  11. Chiral Graphene Quantum Dots.

    PubMed

    Suzuki, Nozomu; Wang, Yichun; Elvati, Paolo; Qu, Zhi-Bei; Kim, Kyoungwon; Jiang, Shuang; Baumeister, Elizabeth; Lee, Jaewook; Yeom, Bongjun; Bahng, Joong Hwan; Lee, Jaebeom; Violi, Angela; Kotov, Nicholas A

    2016-02-23

    Chiral nanostructures from metals and semiconductors attract wide interest as components for polarization-enabled optoelectronic devices. Similarly to other fields of nanotechnology, graphene-based materials can greatly enrich physical and chemical phenomena associated with optical and electronic properties of chiral nanostructures and facilitate their applications in biology as well as other areas. Here, we report that covalent attachment of l/d-cysteine moieties to the edges of graphene quantum dots (GQDs) leads to their helical buckling due to chiral interactions at the "crowded" edges. Circular dichroism (CD) spectra of the GQDs revealed bands at ca. 210-220 and 250-265 nm that changed their signs for different chirality of the cysteine edge ligands. The high-energy chiroptical peaks at 210-220 nm correspond to the hybridized molecular orbitals involving the chiral center of amino acids and atoms of graphene edges. Diverse experimental and modeling data, including density functional theory calculations of CD spectra with probabilistic distribution of GQD isomers, indicate that the band at 250-265 nm originates from the three-dimensional twisting of the graphene sheet and can be attributed to the chiral excitonic transitions. The positive and negative low-energy CD bands correspond to the left and right helicity of GQDs, respectively. Exposure of liver HepG2 cells to L/D-GQDs reveals their general biocompatibility and a noticeable difference in the toxicity of the stereoisomers. Molecular dynamics simulations demonstrated that d-GQDs have a stronger tendency to accumulate within the cellular membrane than L-GQDs. Emergence of nanoscale chirality in GQDs decorated with biomolecules is expected to be a general stereochemical phenomenon for flexible sheets of nanomaterials.

  12. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, J.R.

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  13. Process and catalyst for carbonylating olefins

    DOEpatents

    Zoeller, Joseph Robert

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  14. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1992-01-01

    Low severity coal liquefaction promoted by cyclic olefins offers a means of liquefying coal at low severity conditions. Lower temperature, 350[degrees]C, and lower hydrogen pressure, 500 psi, have been used to perform liquefaction reactions. The presence of the cyclic olefin, hexahydroanthracene, made a substantial difference in the conversion of Illinois No. 6 coal at these low severity conditions. The Researchperformed this quarter was a parametric evaluation of the effect of different parameters on the coal conversion and product distribution from coal. The effect of the parameters on product distribution from hexahydroanthracene was also determined. The work planned for next quarter includes combining the most effective parametric conditions for the low severity reactions and determining their effect. The second part ofthe research performed this quarter involved performing Fourier transform infrared (FTIR) spectroscopy using cyclic olefins. The objective of this study was to determine the feasibility of using FTIR and a heated cell to determine the reaction pathway that occurs in the hydrogen donation reactions from cyclic olefins. The progress made to date includes evaluating the FTIR spectra of cyclic olefins and their expected reaction products. This work is included in this progress report.

  15. Superconductivity in a chiral nanotube

    NASA Astrophysics Data System (ADS)

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-02-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity--unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  16. Chiral anomalies and differential geometry

    SciTech Connect

    Zumino, B.

    1983-10-01

    Some properties of chiral anomalies are described from a geometric point of view. Topics include chiral anomalies and differential forms, transformation properties of the anomalies, identification and use of the anomalies, and normalization of the anomalies. 22 references. (WHK)

  17. Superconductivity in a chiral nanotube

    PubMed Central

    Qin, F.; Shi, W.; Ideue, T.; Yoshida, M.; Zak, A.; Tenne, R.; Kikitsu, T.; Inoue, D.; Hashizume, D.; Iwasa, Y.

    2017-01-01

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity—unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures. PMID:28205518

  18. Superconductivity in a chiral nanotube.

    PubMed

    Qin, F; Shi, W; Ideue, T; Yoshida, M; Zak, A; Tenne, R; Kikitsu, T; Inoue, D; Hashizume, D; Iwasa, Y

    2017-02-16

    Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity-unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

  19. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

  20. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

  1. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

  2. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium salt...

  3. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium salt...

  4. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

  5. 40 CFR 721.5425 - α-Olefin sulfonate, potassium salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false α-Olefin sulfonate, potassium salts... Substances § 721.5425 α-Olefin sulfonate, potassium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as an α-olefin sulfonate, potassium salt (PMN...

  6. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium...

  7. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium...

  8. 40 CFR 721.5450 - α-Olefin sulfonate, sodium salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false α-Olefin sulfonate, sodium salt. 721... Substances § 721.5450 α-Olefin sulfonate, sodium salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as α-olefin sulfonate, sodium...

  9. 40 CFR 721.10241 - Olefinic carbocycle, reaction products with alkoxysilane, sulfurized (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10241 Olefinic carbocycle, reaction... to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  10. 40 CFR 721.10241 - Olefinic carbocycle, reaction products with alkoxysilane, sulfurized (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10241 Olefinic carbocycle, reaction... to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  11. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  12. 40 CFR 721.10242 - Olefinic carbocycle, reaction products with alkoxysilane, polysulfurized (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10242 Olefinic carbocycle, reaction... subject to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  13. 40 CFR 721.10241 - Olefinic carbocycle, reaction products with alkoxysilane, sulfurized (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10241 Olefinic carbocycle, reaction... to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  14. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  15. 40 CFR 721.10242 - Olefinic carbocycle, reaction products with alkoxysilane, polysulfurized (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10242 Olefinic carbocycle, reaction... subject to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  16. 40 CFR 721.10240 - Olefinic carbocycle, reaction products with alkoxysilane (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Olefinic carbocycle, reaction products... Significant New Uses for Specific Chemical Substances § 721.10240 Olefinic carbocycle, reaction products with... substance identified generically as olefinic carbocycle, reaction products with alkoxysilane (PMN...

  17. 40 CFR 721.10242 - Olefinic carbocycle, reaction products with alkoxysilane, polysulfurized (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Olefinic carbocycle, reaction products... SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10242 Olefinic carbocycle, reaction... subject to reporting. (1) The chemical substance identified generically as olefinic carbocycle,...

  18. Effect of process conditions on olefin selectivity during conventional and supercritical Fischer-Tropsch synthesis

    SciTech Connect

    Bukur, D.B.; Lang, X.; Akgerman, A.; Feng, Z.

    1997-07-01

    A precipitated iron catalyst (100 Fe/5 Cu/4.2 K/25 SiO{sub 2} on mass basis) was tested in a fixed-bed reactor under a variety of process conditions during conventional Fischer-Tropsch synthesis (FTS) and supercritical Fischer-Tropsch synthesis (SFTS). In both modes of operation it was found that: total olefin content decreases whereas 2-olefin content increases with either increase in conversion or H{sub 2}/CO molar feed ratio. Total olefin and 2-olefin selectivities were essentially independent of reaction temperature. The effect of conversion was more pronounced during conventional FTS. Comparison of olefin selectivities in the two modes of operation reveals that total olefin content is greater while the 2-olefin content is smaller during SFTS. Also, both the decrease in total olefin content and the increase in 2-olefin content with increase in carbon number (i.e., molecular weight of hydrocarbon products) was significantly less pronounced during SFTS in comparison to the conventional FTS. The obtained results suggest that 1-olefins, and to a smaller extent n-paraffins, are the primary products of FTS. Secondary reactions (isomerization, hydrogenation, and readsorption) of high molecular weight {alpha}-olefins occur to a smaller extent during SFTS, due to higher diffusivities and desorption rates of {alpha}-olefins in the supercritical propane than in the liquid-filled catalyst pores (conventional FTS).

  19. Probing the Origin of Degenerate Metathesis Selectivity via Characterization and Dynamics of Ruthenacyclobutanes Containing Variable NHCs

    PubMed Central

    Keitz, Benjamin K.; Grubbs, Robert H.

    2011-01-01

    The preparation of new phosphonium alkylidene ruthenium metathesis catalysts containing N-heterocyclic carbenes (NHCs) that result in a preference for degenerate metathesis is described. The reaction of the catalysts with ethylene or substrates relevant to ring-closing metathesis (RCM) produced ruthenacyclobutanes that could be characterized by cryogenic NMR spectroscopy. The rate of α/β methylene exchange in ethylene-only ruthenacycles was found to vary widely between ruthenacycles, in some cases being as low as 3.97 s−1 at −30 °C, suggesting that the NHC plays an important role in degenerative metathesis reactions. Attempts to generate RCM-relevant ruthenacycles resulted in the low-yielding formation of a previously unobserved species, which we assign to be a β-alkyl substituted ruthenacycle. Kinetic investigations of the RCM-relevant ruthenacycles in the presence of excess ethylene revealed a large increase in the kinetic barrier of the rate-limiting dissociation of the cyclopentene RCM product compared to previously investigated catalysts. Taken together, these results shed light on the degenerate/productive selectivity differences observed between different metathesis catalysts. PMID:21919449

  20. DFT study of the 1-octene metathesis reaction mechanism with WCl6/C catalytic system.

    PubMed

    Yüksel, Dilek; Düz, Bülent; Sevin, Fatma

    2008-05-22

    A catalytic system consisting of tungsten carbene generated from WCl(6) and an atomic carbon is investigated theoretically for the metathesis of 1-octene at B3LYP/extended LANL2DZ level of DFT. The ground-state geometries and charge distributions of the structures belonging to the reaction mechanism are located. Energetics for the complete set of reactions, involving the formation of the tungsten carbene precatalyst, Cl(4)WCCl(2), the formation of tungsten methylidene and tungsten heptylidene with this precatalyst, and finally productive and degenerative metathesis steps with these alkylidene species are calculated in terms of total electronic energy and thermal energies. The free-energy (ΔG(298)) surfaces of the structures involved in the related reactions are constructed. In addition, solvent effects on the single point energies of the structures are investigated for two different solvents, namely, cyclohexane and chloroform. The results indicate that the formation of the catalytically active heptylidene is energetically favored in comparison to the formation of methylidene, while the degenerative and productive metathesis steps are competitive. In the catalytic cycle, the formation of ethylene is exothermic, while the formation of 7-tetradecene is endothermic. As expected, solvent effects on the metathesis reactions are minor and solvation does not cause any change in the directions of the overall metathesis reactions.

  1. Chiral electroweak currents in nuclei

    DOE PAGES

    Riska, D. O.; Schiavilla, R.

    2017-01-10

    Here, the development of the chiral dynamics based description of nuclear electroweak currents is reviewed. Gerald E. (Gerry) Brown’s role in basing theoretical nuclear physics on chiral Lagrangians is emphasized. Illustrative examples of the successful description of electroweak observables of light nuclei obtained from chiral effective field theory are presented.

  2. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2014-07-15

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  3. Ionic liquids for separation of olefin-paraffin mixtures

    DOEpatents

    Dai, Sheng; Luo, Huimin; Huang, Jing-Fang

    2013-09-17

    The invention is directed to an ionic liquid comprising (i) a cationic portion containing a complex of a silver (I) ion and one or more neutral ligands selected from organoamides, organoamines, olefins, and organonitriles, and (ii) an anionic portion having the chemical formula ##STR00001## wherein m and n are independently 0 or an integer of 1 or above, and p is 0 or 1, provided that when p is 0, the group --N--SO.sub.2--(CF.sub.2).sub.nCF.sub.3 subtended by p is replaced with an oxide atom connected to the shown sulfur atom. The invention is also directed to a method for separating an olefin from an olefin-paraffin mixture by passing the mixture through a layer of the ionic liquid described above.

  4. Adsorptive recovery of olefins from mixtures with paraffins

    SciTech Connect

    Zhuravlev, A.M.; Alekseeva, R.V.; Gerasimenko, E.G.; Alekseev, Yu.A.

    1987-11-01

    The recovery of olefins from mixtures with paraffins by adsorption on synthetic zeolites, aimed at obtaining experimental data for developing a mathematical model, was examined for the purpose of finding a linear olefin source for biodegradable detergents and achieving commensurate reductions in water pollution. Studies were performed under static and dynamic conditions. Test mixtures were prepared from individual hydrocarbons with purities of 98-99.5% by weight. Isotherms of excess sorption and selectivity coefficients for solutions of dodecene mixed with dodecane, octane, cyclohexane, and heptene were determined. Calculations were performed by methods of excess quantities and total content. Data shows the dynamic capacity of the olefins to breakthrough in proportion to their concentration in the original mixture.

  5. Low Severity Coal Liquefaction Promoted by Cyclic Olefins

    SciTech Connect

    Christine W. Curtis

    1998-04-09

    The development of the donor solvent technology for coal liquefaction has drawn a good deal of attention over the last three decades. The search for better hydrogen donors led investigators to a class of compounds known as cyclic olefins. Cyclic olefins are analogues of the conventional hydroaromatic donor species but do not contain aromatic rings. The cyclic olefins are highly reactive compounds which readily release their hydrogen at temperatures of 200 C or higher. Considerable effort has been o expended toward understanding the process of hydrogen donation. Most of this work was conducted in bomb reactors, with product analysis being carried out after the reaction was complete. Efforts directed towards fundamental studies of these reactions in situ are rare. The current work employs a high temperature and high pressure infrared cell to monitor in situ the concentrations of reactants and products during hydrogen release from hydrogen donor compounds.

  6. Metal-free transfer hydrogenation of olefins via dehydrocoupling catalysis

    PubMed Central

    Pérez, Manuel; Caputo, Christopher B.; Dobrovetsky, Roman; Stephan, Douglas W.

    2014-01-01

    A major advance in main-group chemistry in recent years has been the emergence of the reactivity of main-group species that mimics that of transition metal complexes. In this report, the Lewis acidic phosphonium salt [(C6F5)3PF][B(C6F5)4] 1 is shown to catalyze the dehydrocoupling of silanes with amines, thiols, phenols, and carboxylic acids to form the Si-E bond (E = N, S, O) with the liberation of H2 (21 examples). This catalysis, when performed in the presence of a series of olefins, yields the concurrent formation of the products of dehydrocoupling and transfer hydrogenation of the olefin (30 examples). This reactivity provides a strategy for metal-free catalysis of olefin hydrogenations. The mechanisms for both catalytic reactions are proposed and supported by experiment and density functional theory calculations. PMID:25002489

  7. Supramolecular chirality in self-assembled soft materials: regulation of chiral nanostructures and chiral functions.

    PubMed

    Zhang, Li; Qin, Long; Wang, Xiufeng; Cao, Hai; Liu, Minghua

    2014-10-29

    Supramolecular chirality, which arises from the nonsymmetric spatial arrangement of components in the self-assembly systems, has gained great attention owing to its relation to the natural biological structures and the possible new functions in advanced materials. During the self-assembling process, both chiral and achiral components are possible to form chiral nanostructures. Therefore, it becomes an important issue how to fabricate these molecular components into chiral nanostructures. Furthermore, once the chiral nanostructure is obtained, will it show new functions that simple component molecule could not? In this research news, we report our recent development in the regulation of chiral nanostructures in soft gels or vesicle materials. We have further developed several new functions pertaining to the soft gel materials, which single chiral molecules could not perform, such as the chiroptical switch, chiral recognition and the asymmetry catalysis.

  8. Doped Chiral Polymer Metamaterials

    NASA Technical Reports Server (NTRS)

    Park, Cheol (Inventor); Kang, Jin Ho (Inventor); Gordon, Keith L. (Inventor); Sauti, Godfrey (Inventor); Lowther, Sharon E. (Inventor); Bryant, Robert G. (Inventor)

    2017-01-01

    Some implementations provide a composite material that includes a first material and a second material. In some implementations, the composite material is a metamaterial. The first material includes a chiral polymer (e.g., crystalline chiral helical polymer, poly-.gamma.-benzyl-L-glutamate (PBLG), poly-L-lactic acid (PLA), polypeptide, and/or polyacetylene). The second material is within the chiral polymer. The first material and the second material are configured to provide an effective index of refraction value for the composite material of 1 or less. In some implementations, the effective index of refraction value for the composite material is negative. In some implementations, the effective index of refraction value for the composite material of 1 or less is at least in a wavelength of one of at least a visible spectrum, an infrared spectrum, a microwave spectrum, and/or an ultraviolet spectrum.

  9. Creating chiral anomalies

    NASA Astrophysics Data System (ADS)

    Bradlyn, Barry; Cano, Jennifer; Wang, Zhijun; Hirschberger, Max; Ong, N. Phuan; Bernevig, B. Andrei

    Materials with intrinsic Weyl points should present exotic magnetotransport phenomena due to spectral flow between Weyl nodes of opposite chirality - the so-called ``chiral anomaly''. However, to date, the most definitive transport data showing the presence of a chiral anomaly comes from Dirac (not Weyl) materials. These semimetals develop Weyl fermions only in the presence of an externally applied magnetic field, when the four-fold degeneracy is lifted. In this talk we examine Berry phase effects on transport due to the emergence of these field-induced Weyl point and (in some cases) line nodes. We pay particular attention to the differences between intrinsic and field-induced Weyl fermions, from the point of view of kinetic theory. Finally, we apply our analysis to a particular material relevant to current experiments performed at Princeton.

  10. [Chirality and drugs].

    PubMed

    Testa, B; Reist, M; Carrupt, P A

    2000-07-01

    The two enantiomers of a chiral drug may have vastly different pharmacodynamic and pharmacokinetic properties. As a result, the research and development of chiral drugs raises specific problems some of which are discussed here. Thus, various pharmacokinetic interactions may involve two enantiomers, as seen for example when one enantiomer inhibits the metabolism of the other and modifies its effects. A different situation occurs when a third compound stereoselectively inhibits the metabolism of one of the two enantiomers. Another problem examined here results from the lack of configurational stability of some chiral drugs, a little known phenomenon whose consequences can be of pharmacological or pharmaceutical significance depending on the rate of the reaction of racemization or epimerisation. In-depth investigations are needed before choosing between a eutomer or a racemate.

  11. Synthesis and Evaluation of Molybdenum and Tungsten Monoaryloxide Halide Alkylidene Complexes for Z-Selective Cross-Metathesis of Cyclooctene and Z-1,2-Dichloroethylene.

    PubMed

    Lam, Jonathan K; Zhu, Congqing; Bukhryakov, Konstantin V; Müller, Peter; Hoveyda, Amir; Schrock, Richard R

    2016-12-07

    Molybdenum complexes with the general formula Mo(NR)(CHR')(OR″)(Cl)(MeCN) (R = t-Bu or 1-adamantyl; OR″ = a 2,6-terphenoxide) recently have been found to be highly active catalysts for cross-metathesis reactions between Z-internal olefins and Z-1,2-dichloroethylene or Z-(CF3)CH═CH(CF3). In this paper we report methods of synthesizing new potential catalysts with the general formula M(NR)(CHR')(OR″)(Cl)(L) in which M = Mo or W, NR = N-2,6-diisopropylphenyl or NC6F5, and L is a phosphine, a pyridine, or a nitrile. We also test and compare all catalysts in the cross-metathesis of Z-1,2-dichloroethylene and cyclooctene. Our investigations indicate that tungsten complexes are inactive in the test reaction either because the donor is bound too strongly or because acetonitrile inserts into a W═C bond. The acetonitrile or pivalonitrile Mo(NR)(CHR')(OR″)(Cl)(L) complexes are found to be especially reactive because the 14e Mo(NR)(CHR')(OR″)Cl core is accessible through dissociation of the nitrile to a significant extent. Pivalonitrile can be removed (>95%) from Mo(NAr)(CHCMe2Ph)(OHMT)(Cl)(t-BuCN) (Ar = 2,6-diisopropylphenyl; OHMT = 2,6-dimesitylphenoxide) to give 14e Mo(NAr)(CHCMe2Ph)(OHMT)Cl in solution as a mixture of syn and anti (60:40 at 0.015 M) nitrile-free isomers, but these 14e complexes have not yet been isolated in pure form. The syn isomer of Mo(NAr)(CHCMe2Ph)(OHMT)Cl binds pivalonitrile most strongly. Other Mo(NR)(CHR')(OR″)(Cl)(L) complexes can be activated through addition of B(C6F5)3. High stereoselectivities (>98% Z,Z) of ClCH═CH(CH2)6CH═CHCl are not restricted to tert-butylimido or adamantylimido complexes; 96.2% Z selectivity is observed with boron-activated Mo(NC6F5)(CHR')(OHIPT)(Cl)(PPhMe2). So far no Mo═CHCl complexes, which are required intermediates in the test reaction, have been observed in NMR studies at room temperature.

  12. Iridium-catalyzed asymmetric hydrogenation yielding chiral diarylmethines with weakly coordinating or noncoordinating substituents.

    PubMed

    Tolstoy, Päivi; Engman, Mattias; Paptchikhine, Alexander; Bergquist, Jonas; Church, Tamara L; Leung, Abby W-M; Andersson, Pher G

    2009-07-01

    Diarylmethine-containing stereocenters are present in pharmaceuticals and natural products, making the synthetic methods that form these chiral centers are important in industry. We have applied iridium complexes with novel N,P-chelating ligands to the asymmetric hydrogenation of trisubstituted olefins, forming diarylmethine chiral centers in high conversions and excellent enantioselectivities (up to 99% ee) for a broad range of substrates. Our results support the hypothesis that steric hindrance in one specific area of the catalyst is playing a key role in stereoselection, as the hydrogenation of substrates differing little at the prochiral carbon occurred with high enantioselectivity. As a result, excellent stereodiscrimination was obtained even when the prochiral carbon bore, for example, phenyl and p-tolyl groups.

  13. Chiral Liouville gravity

    NASA Astrophysics Data System (ADS)

    Compère, Geoffrey; Song, Wei; Strominger, Andrew

    2013-05-01

    Classical two-dimensional Liouville gravity is often considered in conformal gauge which has a residual left and right Virasoro symmetry algebra. We consider an alternate, chiral, gauge which has a residual right Virasoro Kac-Moody algebra, and no left Virasoro algebra. The Kac-Moody zero mode is the left-moving energy. Dirac brackets of the constrained Hamiltonian theory are derived, and the residual symmetries are shown to be generated by integrals of the conserved chiral currents. The central charge and Kac-Moody level are computed. The possible existence of a corresponding quantum theory is discussed.

  14. Catalytic production of olefin block copolymers via chain shuttling polymerization.

    PubMed

    Arriola, Daniel J; Carnahan, Edmund M; Hustad, Phillip D; Kuhlman, Roger L; Wenzel, Timothy T

    2006-05-05

    We report a catalytic system that produces olefin block copolymers with alternating semicrystalline and amorphous segments, achieved by varying the ratio of alpha-olefin to ethylene in the two types of blocks. The system uses a chain shuttling agent to transfer growing chains between two distinct catalysts with different monomer selectivities in a single polymerization reactor. The block copolymers simultaneously have high melting temperatures and low glass transition temperatures, and therefore they maintain excellent elastomeric properties at high temperatures. Furthermore, the materials are effectively produced in economically favorable, continuous polymerization processes.

  15. Design of an etch-resistant cyclic olefin photoresist

    NASA Astrophysics Data System (ADS)

    Allen, Robert D.; Opitz, Juliann; Wallow, Thomas I.; Di Pietro, Richard A.; Hofer, Donald C.; Jayaraman, Saikumar; Hullihan, Karen A.; Rhodes, Larry F.; Goodall, Brian L.; Shick, Robert A.

    1998-06-01

    In the quest for a high performance 193 nm photoresist with robust plasma etching resistance equivalent to or better than the DUV resists of today, we have focused on the use of cyclic olefin polymers. In this paper, we will discuss monomer synthesis, polymerization approaches, polymer properties and early lithographic results of 193 nm photoresists formulated from cyclic olefin polymeric materials made from a metal-catalyzed addition polymerization process. The goal of this work is to produce a 193 nm photoresist with excellent imaging performance and etch resistance exceeding DUV resists, and in fact approaching novolak-based photoresists.

  16. Catalytic Production of Olefin Block Copolymers via Chain Shuttling Polymerization

    NASA Astrophysics Data System (ADS)

    Arriola, Daniel J.; Carnahan, Edmund M.; Hustad, Phillip D.; Kuhlman, Roger L.; Wenzel, Timothy T.

    2006-05-01

    We report a catalytic system that produces olefin block copolymers with alternating semicrystalline and amorphous segments, achieved by varying the ratio of α-olefin to ethylene in the two types of blocks. The system uses a chain shuttling agent to transfer growing chains between two distinct catalysts with different monomer selectivities in a single polymerization reactor. The block copolymers simultaneously have high melting temperatures and low glass transition temperatures, and therefore they maintain excellent elastomeric properties at high temperatures. Furthermore, the materials are effectively produced in economically favorable, continuous polymerization processes.

  17. Catalytic Intramolecular Ketone Alkylation with Olefins by Dual Activation.

    PubMed

    Lim, Hee Nam; Dong, Guangbin

    2015-12-07

    Two complementary methods for catalytic intramolecular ketone alkylation reactions with unactivated olefins, resulting in Conia-ene-type reactions, are reported. The transformations are enabled by dual activation of both the ketone and the olefin and are atom-economical as stoichiometric oxidants or reductants are not required. Assisted by Kool's aniline catalyst, the reaction conditions can be both pH- and redox-neutral. A broad range of functional groups are thus tolerated. Whereas the rhodium catalysts are effective for the formation of five-membered rings, a ruthenium-based system that affords the six-membered ring products was also developed.

  18. Rheological properties and lubricity of poly-alpha-olefin oils

    SciTech Connect

    Tsvetkov, O.N.; Kolesova, G.E.; Bogdanov, S.K.; Toporishcheva, R.I.

    1988-01-01

    Oils were obtained by polymerization of alpha-olefins with a complex aluminum chloride catalyst, followed by neutralization of the polymerized product, distillation, and hydrogenation. Materials were tested to determine the kinematic viscosity at above- and below-freezing temperatures and dynamic viscosity at below-freezing temperatures. Poly-alpha-olefin oils were obtained at different levels of average molecular weight by varying the conditions of polymerization and distillation. The antiwear properties of petroleum, PAOO, and alkylbenzene oils having equal viscosities and an addition of zinc dialkyldithiophosphate were compared. The dialkylbenzene oil had strong associative-solvation properties with respect to the additive.

  19. Asymmetric catalysis at the mesoscale: gold nanoclusters embedded in chiral self-assembled monolayer as heterogeneous catalyst for asymmetric reactions.

    PubMed

    Gross, Elad; Liu, Jack H; Alayoglu, Selim; Marcus, Matthew A; Fakra, Sirine C; Toste, F Dean; Somorjai, Gabor A

    2013-03-13

    Research to develop highly versatile, chiral, heterogeneous catalysts for asymmetric organic transformations, without quenching the catalytic reactivity, has met with limited success. While chiral supramolecular structures, connected by weak bonds, are highly active for homogeneous asymmetric catalysis, their application in heterogeneous catalysis is rare. In this work, asymmetric catalyst was prepared by encapsulating metallic nanoclusters in chiral self-assembled monolayer (SAM), immobilized on mesoporous SiO2 support. Using olefin cyclopropanation as an example, it was demonstrated that by controlling the SAM properties, asymmetric reactions can be catalyzed by Au clusters embedded in chiral SAM. Up to 50% enantioselectivity with high diastereoselectivity were obtained while employing Au nanoclusters coated with SAM peptides as heterogeneous catalyst for the formation of cyclopropane-containing products. Spectroscopic measurements correlated the improved enantioselectivity with the formation of a hydrogen-bonding network in the chiral SAM. These results demonstrate the synergetic effect of the catalytically active metallic sites and the surrounding chiral SAM for the formation of a mesoscale enantioselective catalyst.

  20. [Synthetic and mechanistic investigation of olefin polymerization catalyzed by early transition metal compounds

    SciTech Connect

    Bercaw, J.E.

    1993-01-01

    During the second year we continued to prepare and characterize organoyttrium and organoscandium compounds for use as catalysts for polymerizing simple olefins and diolefins. Simple, one-component systems are being pursued, suitable for chain initiation, propagation, and termination studies. This document is divided into: dicarbollide derivatives of scandium as potential catalysts; design, synthesis, and characterization of the first isospecific [alpha] olefin polymerization catalysts; polymerization of [alpha] olefins and 1,5- hexadiene using organoscandium catalysts; and attempted preparations of diastereomeric Nb and Ta olefin/hydride and olefin/alkyl derivatives.

  1. Electrochemistry for biofuel generation: transformation of fatty acids and triglycerides to diesel-like olefin/ether mixtures and olefins.

    PubMed

    dos Santos, Tatiane R; Harnisch, Falk; Nilges, Peter; Schröder, Uwe

    2015-03-01

    Electroorganic synthesis can be exploited for the production of biofuels from fatty acids and triglycerides. With Coulomb efficiencies (CE) of up to 50 %, the electrochemical decarboxylation of fatty acids in methanolic and ethanolic solutions leads to the formation of diesel-like olefin/ether mixtures. Triglycerides can be directly converted in aqueous solutions by using sonoelectrochemistry, with olefins as the main products (with a CE of more than 20 %). The latter reaction, however, is terminated at around 50 % substrate conversion by the produced side-product glycerol. An energy analysis shows that the electrochemical olefin synthesis can be an energetically competitive, sustainable, and--in comparison with established processes--economically feasible alternative for the exploitation of fats and oils for biofuel production. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Well-defined silica-supported zirconium-imido complexes mediated heterogeneous imine metathesis.

    PubMed

    Hamzaoui, Bilel; Pelletier, Jérémie D A; Abou-Hamad, Edy; Basset, Jean-Marie

    2016-03-28

    Upon prolonged thermal exposure under vacuum, a well-defined single-site surface species [([triple bond, length as m-dash]Si-O-)Zr(NEt2)3] () evolves into an ethylimido complex [([triple bond, length as m-dash]Si-O-)Zr([double bond, length as m-dash]NEt)NEt2] (). Reactions of with an imine substrate result in imido/imine ([double bond, length as m-dash]NRi, R: Et, Ph) exchange (metathesis) with the formation of [([triple bond, length as m-dash]Si-O-)Zr([double bond, length as m-dash]NPh)NEt2] (). Compounds and effectively catalyze imine/imine cross-metathesis and are thus considered as the first heterogeneous catalysts active for imine metathesis.

  3. Chiral symmetry in quarkyonic matter

    SciTech Connect

    Kojo, T.

    2012-05-15

    The 1/N{sub c} expansion classifies nuclear matter, deconfined quark matter, and Quarkyonic matter in low temperature region. We investigate the realization of chiral symmetry in Quarkyonic matter by taking into account condensations of chiral particle-hole pairs. It is argued that chiral symmetry and parity are locally violated by the formation of chiral spirals, <{psi}-bar exp (2i{mu}{sub q} z{gamma}{sup 0} {gamma}{sup z}){psi}> . An extension to multiple chiral spirals is also briefly discussed.

  4. Synthesis of nanosized silicon particles by a rapid metathesis reaction

    NASA Astrophysics Data System (ADS)

    Won, C. W.; Nersisyan, H. H.; Won, H. I.; Lee, H. H.

    2009-11-01

    A solid-state rapid metathesis reaction was performed in a bed of sodium silicofluoride (Na 2SiF 6) and sodium azide (NaN 3) powders diluted with sodium fluoride (NaF), to produce silicon nanoparticles. After a local ignition of Na 2SiF 6+4NaN 3+ kNaF mixture (here k is mole number of NaF), the reaction proceeded in a self-sustaining combustion mode developing high temperatures (950-1000 °C) on very short time scales (a few seconds). Silicon nanoparticles prepared by the combustion process was easily separated from the salt byproducts by simple washing with distilled water. The structural and morphological studies on the nanoparticles were carried out using X-ray diffractometer (XRD) and field emission scanning electron microscope (FESEM). The mean size of silicon particles calculated from the FESEM image was about 37.75 nm. FESEM analysis also shows that the final purified product contains a noticeable amount of silicon fibers, dendrites and blocks, along with nanoparticles. The mechanism of Si nanostructures formation is discussed and a simple model for interpretation of experimental results is proposed.

  5. Oxidation-triggered ring-opening metathesis polymerization.

    PubMed

    Savka, Roman; Foro, Sabine; Gallei, Markus; Rehahn, Matthias; Plenio, Herbert

    2013-08-05

    Eight new N-Hoveyda-type complexes were synthesized in yields of 67-92 % through reaction of [RuCl2 (NHC)(Ind)(py)] (NHC=1,3-bis(2,4,6-trimethylphenylimidazolin)-2-ylidene (SIMes) or 1,3-bis(2,6-diisopropylphenylimidazolin)-2-ylidene (SIPr), Ind=3-phenylindenylid-1-ene, py=pyridine) with various 1- or 1,2-substituted ferrocene compounds with vinyl and amine or imine substituents. The redox potentials of the respective complexes were determined; in all complexes an iron-centered oxidation reaction occurs at potentials close to E=+0.5 V. The crystal structures of the reduced and of the respective oxidized Hoveyda-type complexes were determined and show that the oxidation of the ferrocene unit has little effect on the ruthenium environment. Two of the eight new complexes were found to be switchable catalysts, in that the reduced form is inactive in the ring-opening metathesis polymerization of cis-cyclooctene (COE), whereas the oxidized complexes produce polyCOE. The other complexes are not switchable catalysts and are either inactive or active in both reduced and oxidized states. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Organic and composite aerogels through ring opening metathesis polymerization (ROMP)

    NASA Astrophysics Data System (ADS)

    Mohite, Dhairyashil P.

    Aerogels are open-cell nanoporous materials, unique in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. Those exceptional properties stem from their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles), but they also come at a cost: low mechanical strength. This issue has been resolved by crosslinking silica aerogels with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework by covalent bridging elementary building blocks. However, "assuming" is not enough: for correlating nanostructure with bulk material properties, it is important to know the exact location of the polymer on the aerogel backbone. For that investigation, we synthesized a new norbornene derivative of triethoxysilane (Si-NAD) that can be attached to skeletal silica nanoparticles. Those norbornene-modified silica aerogels were crosslinked with polynorbornene by ring opening metathesis polymerization (ROMP). The detailed correlation between nanostructure and mechanical strength was probed with a wide array of characterization methods ranging from molecular to bulk through nano. Subsequently, it was reasoned that since the polymer dominates the exceptional mechanical properties of polymer crosslinked aerogels, purely organic aerogels with the same nanostructure and interparticle connectivity should behave similarly. That was explored and confirmed by: (a) synthesis of a difunctional nadimide monomer (bis-NAD), and preparation of robust polyimide aerogels by ROMP of its norbornene end-caps; and, (b) synthesis of dimensionally stable ROMP-derived polydicyclopentadiene aerogels by grafting the nanostructure with polymethylmethacrylate (PMMA) via free radical chemistry.

  7. Effects of vanadium and zinc promotion on the olefin selectivity of iron Fischer-Tropsch catalysts

    SciTech Connect

    Saglam, M.

    1989-02-01

    The aim in most of the studies on Fischer-Tropsch synthesis has been the selective production of olefins, which are the raw materials of petrochemical industry. In this study, the effects of V and Zn addition, separately or together in the form of their oxides, to Fe catalysts obtained through precipitation on the olefin selectivity of the catalysts have been investigated. The experiments have been done in a fixed-bed reactor at different temperatures and pressures with various ratios of H/sub 2//CO. The addition of V separately (catalyst 2) or together with Zn (catalyst 1) has greatly increased the olefin selectivity of Fe catalyst. So the amount of olefin in hydrocarbon fractions has reached over 80%. Besides, the ..cap alpha..-olefin parts in olefin fractions have gone over 90%. But the addition of Zn separately has been less effective on the olefin selectivity of the catalyst.

  8. Mechanism of Olefin Asymmetric Hydrogenation Catalyzed by Iridium Phosphino-Oxazoline: A Pair Natural Orbital Coupled Cluster Study.

    PubMed

    Sparta, Manuel; Riplinger, Christoph; Neese, Frank

    2014-03-11

    Since the development of chiral phosphino-oxazoline iridium catalysts, which hydrogenate unfunctionalized alkenes enantioselectively, the asymmetric hydrogenation of prochiral olefins has become important in the production of chiral compounds. For the last 10 years, details of the mechanism, including formal oxidation state assignment of the metal center and the nature of intermediates and transition states have been debated. Various contributions have been given from a theoretical point of view, but due to the size of the structures, these have been forced to rely on density functional theory (DFT) methods. In our investigation of the catalytic cycle, we employ both DFT and a correlated ab initio method, namely, the newly implemented domain-based local pair natural orbital coupled-cluster theory with single and double excitations and the inclusion of perturbative triples correction (DLPNO-CCSD(T)). Our results show that the most likely active paths involve the formation of an intermediate Ir(V) species. Furthermore, we have been able to predict the absolute configuration of the major products, and where comparison to experiment is possible, the results of our calculations agree with the enantiomeric excess obtained from hydrogenating five prochiral substrates. This work also shows that it is now possible to study catalytic reactions with untruncated models (having up to 88 atoms) at the CCSD(T) level of theory.

  9. Tandem ring-closing metathesis/transfer hydrogenation: practical chemoselective hydrogenation of alkenes.

    PubMed

    Connolly, Timothy; Wang, Zhongyu; Walker, Michael A; McDonald, Ivar M; Peese, Kevin M

    2014-09-05

    An operationally simple chemoselective transfer hydrogenation of alkenes using ruthenium metathesis catalysts is presented. Of great practicality, the transfer hydrogenation reagents can be added directly to a metathesis reaction and effect hydrogenation of the product alkene in a single pot at ambient temperature without the need to seal the vessel to prevent hydrogen gas escape. The reduction is applicable to a range of alkenes and can be performed in the presence of aryl halides and benzyl groups, a notable weakness of Pd-catalyzed hydrogenations. Scope and mechanistic considerations are presented.

  10. Paternò-Büchi reaction between furan and heterocyclic aldehydes: oxetane formation vs. metathesis.

    PubMed

    D'Auria, Maurizio; Racioppi, Rocco; Viggiani, Licia

    2010-08-01

    The photochemical reaction of 2-substituted heterocyclic aldehydes with furan gave the corresponding exo oxetane derivatives through the excited triplet state. However, in situ the oxetane derivatives were converted through a metathesis reaction into the corresponding Z,E-butadienyl formate derivatives. On the contrary, 3-substituted heterocyclic aldehydes gave the corresponding exo oxetane derivatives. The effect of 2-substituted heterocyclic ring in order to facilitate the metathesis reaction is explained considering the possible participation of the pi aromatic orbitals in the oxetane C-O bond cleavage.

  11. Synthesis and Trapping of Iminoboranes by M=B/C=N Bond Metathesis.

    PubMed

    Nutz, Marco; Borthakur, Bitupon; Dewhurst, Rian D; Deißenberger, Andrea; Dellermann, Theresa; Schäfer, Marius; Krummenacher, Ivo; Phukan, Ashwini K; Braunschweig, Holger

    2017-06-26

    Although the metathesis of metal-boron double bonds with elemental chalcogenides is an established process, no similar reactivity has been observed with element-nitrogen bonds. Such a reaction would provide a new route to iminoborane compounds (RB≡NR'), which have recently experienced renewed synthetic interest. Herein, we present the first observation of M=B/C=N metathesis reactions, which led to the isolation of a stable iminoborane in addition to further iminoborane cycloaddition products. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Tandem enyne metathesis-Diels-Alder reaction for construction of natural product frameworks.

    PubMed

    Rosillo, Marta; Domínguez, Gema; Casarrubios, Luis; Amador, Ulises; Pérez-Castells, Javier

    2004-03-19

    Enynes connected through aromatic rings are used as substrates for metathesis reactions. The reactivity of three ruthenium carbene complexes is compared. The resulting 1,3-dienes are suitable precursors of polycyclic structures via a Diels-Alder process. Some domino RCM-Diels-Alder reactions are performed, suggesting a possible beneficial effect of the ruthenium catalyst in the cycloaddition process. Other examples require Lewis acid cocatalyst. When applied to aromatic ynamines or enamines, a new synthesis of vinylindoles is achieved. Monitorization of several metathesis reactions with NMR shows the different behavior for ruthenium catalysts. New carbenic species are detected in some reactions with an important dependence on the solvent used.

  13. Chiral fiber sensors

    NASA Astrophysics Data System (ADS)

    Kopp, Victor I.; Churikov, Victor M.; Singer, Jonathan; Neugroschl, Daniel; Genack, Azriel Z.

    2010-04-01

    We have fabricated a variety of chiral fiber sensors by twisting one or more standard or custom optical fibers with noncircular or nonconcentric core as they pass though a miniature oven. The resulting structures are as stable as the glass material and can be produced with helical pitch ranging from microns to hundreds of microns. The polarization selectivity of the chiral gratings is determined by the geometry of the fiber cross section. Single helix structures are polarization insensitive, while double helix gratings interact only with a single optical polarization component. Both single and double helix gratings may function as a fiber long period grating, coupling core and cladding modes or as a diffraction grating scattering light from the fiber core out of the fiber. The resulting dips in the transmission spectrum are sensitive to fiber elongation, twist and temperature, and (in the case of the long period gratings) to the refractive index of the surrounding medium. The suitability of chiral gratings for sensing temperature, elongation, twist and liquid levels will be discussed. Gratings made of radiation sensitive glass can be used to measure the cumulative radiation dose, while gratings made of radiation-hardened glass are suitable for stable sensing of the environment in nuclear power plants. Excellent temperature stability up to 900°C is found in pure silica chiral diffraction grating sensors.

  14. Tuning spontaneous radiation of chiral molecules by asymmetric chiral nanoparticles.

    PubMed

    Guzatov, Dmitry V; Klimov, Vasily V; Chan, Hsun-Chi; Guo, Guang-Yu

    2017-03-20

    We have obtained analytical expressions for the radiative decay rate of the spontaneous emission of a chiral molecule located near a dielectric spherical particle with a chiral nonconcentric spherical shell made of a bi-isotropic material. Our numerical and graphical analyses show that material composition, thickness and degree of non-concentricity of the shell can influence significantly the spontaneous radiation of the chiral molecule. In particular, the radiative decay rates can differ in orders of magnitude for a chiral molecule located near the thin and thick parts of a nonconcentric shell as well as near a concentric shell made of chiral metamaterial. We also find that the radiative decay rates of the "right" and "left" chiral molecule enantiomers located near a nanoparticle with a chiral metamaterial shell can differ pronouncedly from each other. Our findings therefore suggest a way to tune the spontaneous emission of chiral molecules by varying the material composition, thickness and degree of non-concentricity of the shell in the nearby composite nanoparticle and also to enhance the chirality selection of chiral molecules in racemic mixtures.

  15. Interweaving chiral spirals

    NASA Astrophysics Data System (ADS)

    Kojo, Toru; Hidaka, Yoshimasa; Fukushima, Kenji; McLerran, Larry D.; Pisarski, Robert D.

    2012-02-01

    We elaborate how to construct interweaving chiral spirals in (2+1) dimensions, defined as a superposition of chiral spirals oriented in different directions. We divide a two-dimensional Fermi sea into distinct wedges, characterized by the opening angle 2 Θ and depth Q≃p, where p is the Fermi momentum. In each wedge, the energy is lowered by forming a single chiral spiral. The optimal values for Θ and Q are chosen by balancing this gain in energy versus the cost of deforming the Fermi surface (which dominates at large Θ) and patch-patch interactions (dominant at small Θ). Using a non-local four-Fermi interaction model, we estimate the gain and cost in energy by expanding in terms of 1/N (where N is the number of colors), Λ/Q, and Θ. Due to a form factor in our non-local model, at small 1/N the mass gap (chiral condensate) is large, and the interaction among quarks and the condensate local in momentum space. Consequently, interactions between different patches are localized near their boundaries, and it is simple to embed many chiral spirals. We identify the dominant and subdominant terms at high density and categorize formulate an expansion in terms of Λ/Q or Θ. The kinetic term in the transverse directions is subdominant, so that techniques from (1+1)-dimensional systems can be utilized. To leading order in 1/N and Λ/Q, the total gain in energy is ˜pΛQCD2 with Θ˜(. Since Θ decreases with increasing p, there should be phase transitions associated with the change in the wedge number. We also argue the effects of subdominant terms at lower density where the large- N approximation is more reliable.

  16. Bio-olefins from unsaturated fatty acids via tandem catalysis

    USDA-ARS?s Scientific Manuscript database

    A new catalytic route to bio-olefins from unsaturated fatty acids will be described. At the heart of the process, the catalyst apparently functions in a tandem mode by both dynamically isomerizing the positions of double bonds in an aliphatic chain and, subsequently, decarboxylating specific isomers...

  17. ULTRASOUND-ASSISTED ORGANIC SYNTHESIS: ALCOHOL OXIDATION AND OLEFIN EPOXIDATION

    EPA Science Inventory

    Ultrasound-assisted Organic Synthesis: Alcohol Oxidation and Olefin Epoxidation

    Unnikrishnan R Pillai, Endalkachew Sahle-Demessie , Vasudevan Namboodiri, Quiming Zhao, Juluis Enriquez
    U.S. EPA , 26 W. Martin Luther King Dr. , Cincinnati, OH 45268
    Phone: 513-569-773...

  18. Palladium-Catalyzed 1,1- Aryloxygenation of Terminal Olefins

    PubMed Central

    Satterfield, Andrew D.; Kubota, Asako; Sanford, Melanie S.

    2011-01-01

    This paper describes the 1,1-arylacetoxylation of diverse α-olefins using organostannanes and hypervalent iodine oxidants. The reaction provides a convergent approach for generating a C–C and a C-O bond as well as a new stereocenter in a single catalytic transformation. PMID:21291210

  19. ULTRASOUND-ASSISTED ORGANIC SYNTHESIS: ALCOHOL OXIDATION AND OLEFIN EPOXIDATION

    EPA Science Inventory

    Ultrasound-assisted Organic Synthesis: Alcohol Oxidation and Olefin Epoxidation

    Unnikrishnan R Pillai, Endalkachew Sahle-Demessie , Vasudevan Namboodiri, Quiming Zhao, Juluis Enriquez
    U.S. EPA , 26 W. Martin Luther King Dr. , Cincinnati, OH 45268
    Phone: 513-569-773...

  20. Feedstock-flexible olefins plants can be efficient

    SciTech Connect

    DeHaan, S.

    1983-09-26

    Factors such as relative price, political policies, the world economic recovery, and propylene and other byproduct markets will determine the best future olefin feedstock. The choice of feedstocks will have a significant impact on plant investment by increasing sizes and/or requiring additional processing steps. The European and Japanese olefins industries have traditionally been based on liquid feedstock, naphthas, and gas oils. The U.S. industry's base was nearly totally natural gas derived ethane and LPG until a surge of interest in liquid feedstocks in the 1970s. Today, about one-third of the U.S. ethylene plant capacity is designed to utilize liquid feedstocks. The European and Japanese industries remain predominantly liquid feed based. Summary. While a multi-feed olefins plant is a complex entity, a properly conceived olefins design can provide for a wide range of feedstock flexibility, without significantly compromising overall plant efficiency. The optimization of any such operation is an extremely detailed and difficult problem. Therefore, it warrants the use of the best available digital technology. A sophisticated simulator/optimizer can provide valuable guidance to plant operators. Well trained operators assisted by a reliable closed-loop computer control system and a plant optimizer can greatly enhance plant profitability by maintaining optimum performance and maximum on-stream time.

  1. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    DOEpatents

    Marks, Tobin J.; Ja, Li; Yang, Xinmin

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

  2. Circumventing Diffusion in Kinetically Controlled Solid-State Metathesis Reactions.

    PubMed

    Martinolich, Andrew J; Kurzman, Joshua A; Neilson, James R

    2016-08-31

    Solid-state diffusion is often the primary limitation in the synthesis of crystalline inorganic materials and prevents the potential discovery and isolation of new materials that may not be the most stable with respect to the reaction conditions. Synthetic approaches that circumvent diffusion in solid-state reactions are rare and often allow the formation of metastable products. To this end, we present an in situ study of the solid-state metathesis reactions MCl2 + Na2S2 → MS2 + 2 NaCl (M = Fe, Co, Ni) using synchrotron powder X-ray diffraction and differential scanning calorimetry. Depending on the preparation method of the reaction, either combining the reactants in an air-free environment or grinding homogeneously in air before annealing, the barrier to product formation, and therefore reaction pathway, can be altered. In the air-free reactions, the product formation appears to be diffusion limited, with a number of intermediate phases observed before formation of the MS2 product. However, grinding the reactants in air allows NaCl to form directly without annealing and displaces the corresponding metal and sulfide ions into an amorphous matrix, as confirmed by pair distribution function analysis. Heating this mixture yields direct nucleation of the MS2 phase and avoids all crystalline binary intermediates. Grinding in air also dissipates a large amount of lattice energy via the formation of NaCl, and the crystallization of the metal sulfide is a much less exothermic process. This approach has the potential to allow formation of a range of binary, ternary, or higher-ordered compounds to be synthesized in the bulk, while avoiding the formation of many binary intermediates that may otherwise form in a diffusion-limited reaction.

  3. Pressure-induced metathesis reaction to sequester Cs.

    PubMed

    Im, Junhyuck; Seoung, Donghoon; Lee, Seung Yeop; Blom, Douglas A; Vogt, Thomas; Kao, Chi-Chang; Lee, Yongjae

    2015-01-06

    We report here a pressure-driven metathesis reaction where Ag-exchanged natrolite (Ag16Al16Si24O80·16H2O, Ag-NAT) is pressurized in an aqueous CsI solution, resulting in the exchange of Ag(+) by Cs(+) in the natrolite framework forming Cs16Al16Si24O80·16H2O (Cs-NAT-I) and, above 0.5 GPa, its high-pressure polymorph (Cs-NAT-II). During the initial cation exchange, the precipitation of AgI occurs. Additional pressure and heat at 2 GPa and 160 °C transforms Cs-NAT-II to a pollucite-related, highly dense, and water-free triclinic phase with nominal composition CsAlSi2O6. At ambient temperature after pressure release, the Cs remains sequestered in a now monoclinic pollucite phase at close to 40 wt % and a favorably low Cs leaching rate under back-exchange conditions. This process thus efficiently combines the pressure-driven separation of Cs and I at ambient temperature with the subsequent sequestration of Cs under moderate pressures and temperatures in its preferred waste form suitable for long-term storage at ambient conditions. The zeolite pollucite CsAlSi2O6·H2O has been identified as a potential host material for nuclear waste remediation of anthropogenic (137)Cs due to its chemical and thermal stability, low leaching rate, and the large amount of Cs it can contain. The new water-free pollucite phase we characterize during our process will not display radiolysis of water during longterm storage while maintaining the Cs content and low leaching rate.

  4. Optical properties of chiral nanotubes

    NASA Astrophysics Data System (ADS)

    Cecilia, Noguez; Román-Velázquez Carlos, E.; Ariadna, Sánchez; Montes Lilia, Meza

    2004-03-01

    A recent theoretical model [1] is applied to study the optical properties chiral nanostructures like carbon nanotubes. We calculate the Circular Dichroism (CD) spectra for carbon nanotubes with different chirality. The calculated CD spectra show features that allow us to distinguish between nanotubes with different indexes of chirality. Other nanostructures, like chiral fullerenes are also investigated.These results provide theoretical support for the quantification of chirality and its measurement, using the CD lineshapes of chiral. This work has been partly financed by CONACyT grant No. 36651-E and by DGAPA-UNAM grants No. IN104201. [1] C. E. Roman-Velazquez, et al., J. of Phys. Chem. B (Letter) 107, 12035 (2003)

  5. Modes of structurally chiral lasers

    NASA Astrophysics Data System (ADS)

    Topf, René D. M.; McCall, Martin W.

    2014-11-01

    We employ coupled wave theory to enumerate the lasing modes of structurally chiral lasers. The elliptical modes are shown to be fundamentally distinct from those of a scalar distributed feedback laser. High threshold modes are shown to lase with the opposite chirality as the active medium, in contrast to their low-threshold counterparts that lase with the same chirality as the active medium. The lasing mode structure suggests the intriguing possibility of dynamically changing the polarization handedness of a chiral laser, as well as the possibility of lasing within the forbidden band-gap region. These observations arise from the fundamental interplay between the distributed chirality-preserving reflections within the active medium and the localized chirality-reversing reflections at the medium's boundaries.

  6. Ring-Closing Metathesis: An Advanced Guided-Inquiry Experiment for the Organic Laboratory

    ERIC Educational Resources Information Center

    Schepmann, Hala G.; Mynderse, Michelle

    2010-01-01

    The design and implementation of an advanced guided-inquiry experiment for the organic laboratory is described. Grubbs's second-generation catalyst is used to effect the ring-closing metathesis of diethyl diallylmalonate. The reaction is carried out under an inert atmosphere at room temperature and monitored by argentic TLC. The crude reaction is…

  7. Synthesis of the Caeliferins, elicitors of plant immune responses: accessing Lipophilic natural products via cross metathesis

    USDA-ARS?s Scientific Manuscript database

    We report a cross metathesis- (CM-) based syn-thesis of the caeliferins, a family of sulfooxy fatty acids that elicit plant immune responses. Unexpectedly, detailed NMR-spectroscopic and mass spectrometric analyses of CM reaction mixtures revealed extensive isomerization and homologation of starting...

  8. Cis-Selective Ring-Opening Metathesis Polymerization with Ruthenium Catalysts

    PubMed Central

    Keitz, Benjamin K.; Fedorov, Alexey; Grubbs, Robert H.

    2012-01-01

    Using a C-H activated, ruthenium-based metathesis catalyst, the cis selective ROMP of several monocyclic alkenes, as well as norbornene and oxanorbornene-type monomers is reported. The cis content of the isolated polymers depended heavily on monomer structure and temperature. By lowering the temperature, cis content as high as 96% could be obtained. PMID:22239675

  9. Capture and metathesis-based release of potassium salts by a multitopic ion receptor

    SciTech Connect

    Kim, Sung Kuk; Hay, Benjamin P.; Kim, Jong Seung; Moyer, Bruce A.; Sessler, Jonathan L.

    2013-01-25

    Here, we report that the multitopic ion-pair receptor 2 is able to recognize and extract various cesium and potassium salts via three different ion recognition modes. Furthermore, it is capable of extracting and then releasing KNO3via ion-pair metathesis with CsClO4, allowing KNO3 recovery.

  10. Bridgehead vicinal diallylation of norbornene derivatives and extension to propellane derivatives via ring-closing metathesis

    PubMed Central

    Gunta, Rama

    2016-01-01

    Summary Here, we report a simple synthetic strategy to the bridgehead vicinal diallylation of norbornene derivatives. These substrates are useful to generate propellanes via ring-closing metathesis. Single-crystal X-ray diffraction analysis of four compounds led to the realization of configurational correction of earlier reported molecules. PMID:27829894

  11. A Fluorous-Tagged Linker from Which Small Molecules Are Released by Ring-Closing Metathesis

    PubMed Central

    Leach, Stuart G.; Cordier, Christopher J.; Morton, Daniel; McKiernan, Gordon J.; Warriner, Stuart; Nelson, Adam

    2008-01-01

    A fluorous-tagged linker for the parallel synthesis of small- and medium-ring and macrocyclic nitrogen heterocycles using ring-closing metathesis is described. The linker was designed such that “cyclization-release” of the cyclic heterocyclic products was coupled with liberation of the active catalyst. The design of the linker was validated using a non-fluorous-tagged model. A wide range of unsaturated alcohols were used as reagents to functionalize a fluorous-tagged sulfonamide,(Z)-{N-[4-(2-(N’-3,3,4,4,5,5,6,6,7,7,8,8,9,9,-10,10,10-heptadecafluorodecyl)-4-methylsulfonamido)methylallyloxy]but-2-enyl}-2-nitrobenzene-sulfonamide, using Fukuyama-Mitsunobu reactions; in each case, fluorous-solid-phase extraction (F-SPE) was used to purify the functionalized linker from the excess reagents. In general, the “cyclization-release” of cyclic products was triggered using a light-fluorous tagged derivative of the Grubbs-Hoveyda second-generation catalyst. After the metathesis step, F-SPE was used to purify released cyclic compounds from the fluorous-tagged linker and the fluorous-tagged catalyst. The scope and limitations of the approach were determined using a range of substrates which probed different aspects of the functionalization and metathesis steps. In the study as a whole, a wide range of small- and medium-ring and macrocyclic nitrogen heterocycles were prepared using polyene and polyenyne metathesis cascades. PMID:18327951

  12. The Acquisition of Consonant Feature Sequences: Harmony, Metathesis, and Deletion Patterns in Phonological Development

    ERIC Educational Resources Information Center

    Gerlach, Sharon Ruth

    2010-01-01

    This dissertation examines three processes affecting consonants in child speech: harmony (long-distance assimilation) involving major place features as in "coat" [kouk]; long-distance metathesis as in "cup" [p[wedge]k]; and initial consonant deletion as in "fish" [is]. These processes are unattested in adult phonology, leading to proposals for…

  13. Ring-Closing Metathesis: An Advanced Guided-Inquiry Experiment for the Organic Laboratory

    ERIC Educational Resources Information Center

    Schepmann, Hala G.; Mynderse, Michelle

    2010-01-01

    The design and implementation of an advanced guided-inquiry experiment for the organic laboratory is described. Grubbs's second-generation catalyst is used to effect the ring-closing metathesis of diethyl diallylmalonate. The reaction is carried out under an inert atmosphere at room temperature and monitored by argentic TLC. The crude reaction is…

  14. The Acquisition of Consonant Feature Sequences: Harmony, Metathesis, and Deletion Patterns in Phonological Development

    ERIC Educational Resources Information Center

    Gerlach, Sharon Ruth

    2010-01-01

    This dissertation examines three processes affecting consonants in child speech: harmony (long-distance assimilation) involving major place features as in "coat" [kouk]; long-distance metathesis as in "cup" [p[wedge]k]; and initial consonant deletion as in "fish" [is]. These processes are unattested in adult phonology, leading to proposals for…

  15. Synthesis of Cycloparaphenyleneacetylene via Alkyne Metathesis: C70 Complexation and Copper-Free Triple Click Reaction.

    PubMed

    Lee, Semin; Chénard, Etienne; Gray, Danielle L; Moore, Jeffrey S

    2016-10-10

    Alkyne metathesis provided an efficient macrocyclization route to a cycloparaphenyleneacetylene derivative in high yield. The cavity size was suitably matched for C70 which was tightly bound in an induced-fit fashion. The strain on the alkynyl bonds enabled a copper-free, three-fold azide-alkyne cycloaddi-tion at 50 °C.

  16. ENANTIOMER-SPECIFIC EFFECTS OF CHIRAL POLLUTANTS

    EPA Science Inventory

    Enantiomers, the mirror image isomers of chiral pollutants, are known to be selective in their interaction with other chiral molecules, including enzymes and other biochemicals. Considerable research has shown, for example, that chiral pesticides are degraded selectively by micr...

  17. Chiral conical diffraction

    NASA Astrophysics Data System (ADS)

    Berry, M. V.; Jeffrey, M. R.

    2006-05-01

    The geometrical and wave optics are explored for light emerging from a slab of transparent biaxial crystal with optical activity (chirality), for an incident beam directed along the optic axis. The geometrical optics, here derived from Hamilton's principle, is dominated by a circularly symmetric cusped caustic surface ('spun cusp') threaded by an axial focal line. In wave optics, formulated exactly in the paraxial approximation in terms of integrals previously obtained by Belsky and Stepanov and here derived using a unitary evolution operator, the field is determined by two dimensionless parameters. The geometrical features are decorated by interference, here explored in the focal image plane (where the Poggendorff rings of the non-chiral case are in sharpest focus) and along the axis. Asymptotic approximations are derived in terms of the geometrical optics rays (including interference and evanescent waves), near the spun cusp, and uniformly across the caustic surface far from the cusp.

  18. Chiral symmetry and pentaquarks

    SciTech Connect

    Dmitri Diakonov

    2004-07-01

    Spontaneous chiral symmetry breaking, mesons and baryons are illustrated in the language of the Dirac theory. Various forces acting between quarks inside baryons are discussed. I explain why the naive quark models typically overestimate pentaquark masses by some 500 MeV and why in the fully relativistic approach to baryons pentaquarks turn out to be light. I discuss briefly why it can be easier to produce pentaquarks at low than at high energies.

  19. Chiral Dynamics 2006

    NASA Astrophysics Data System (ADS)

    Ahmed, Mohammad W.; Gao, Haiyan; Weller, Henry R.; Holstein, Barry

    2007-10-01

    pt. A. Plenary session. Opening remarks: experimental tests of chiral symmetry breaking / A. M. Bernstein. [Double pie symbols] scattering / H. Leutwyler. Chiral effective field theory in a [Triangle]-resonance region / V. Pascalutsa. Some recent developments in chiral perturbation theory / Ulf-G. Mei ner. Chiral extrapolation and nucleon structure from the lattice / R.D. Young. Recent results from HAPPEX / R. Michaels. Chiral symmetries and low energy searches for new physics / M.J. Ramsey-Musolf. Kaon physics: recent experimental progress / M. Moulson. Status of the Cabibbo angle / V. Cirigliano. Lattice QCD and nucleon spin structure / J.W. Negele. Spin sum rules and polarizabilities: results from Jefferson lab / J-P Chen. Compton scattering and nucleon polarisabilities / Judith A. McGovern. Virtual compton scattering at MIT-bates / R. Miskimen. Physics results from the BLAST detector at the BATES accelerator / R.P. Redwine. The [Pie sympbol]NN system, recent progress / C. Hanhart. Application of chiral nuclear forces to light nuclei / A. Nogga. New results on few-body experiments at low energy / Y. Nagai. Few-body lattice calculations / M.J. Savage. Research opportunities at the upgraded HI?S facility / H.R. Weller -- pt. B. Goldstone boson dynamics. Working group summary: Goldstone Boson dynamics / G. Colangelo and S. Giovannella. Recent results on radiative Kaon decays from NA48 and NA48/2 / S.G. López. Cusps in K-->3 [Pie symbol] decays / B. Kubis. Recent KTeV results on radiative Kaon decays / M.C. Ronquest. The [Double pie symbols] scattering amplitude / J.R. Peláez. Determination of the Regge parameters in the [Double pie symbols] scattering amplitude / I. Caprini. e+e- Hadronic cross section measurement at DA[symbol]NE with the KLOE detector / P. Beltrame. Measurement of the form factors of e+e- -->2([Pie symbol]+[Pie symbol]-), pp and the resonant parameters of the heavy charmonia at BES / H. Hu. Measurement of e+e- multihadronic cross section below 4

  20. [Chirality and drugs].

    PubMed

    Husson, H P

    1997-01-01

    Following a brief historical review of the notion of chirality, the importance of the relationship between pharmacological activity and the enantiomeric forms of drugs is indicated. Different approaches for the preparation of optically-pure molecules are discussed, and an original strategy, known as the "CN(R,S) method", is described. To conclude, an application of this method in the synthesis of a pharmacologically-active molecule is presented.

  1. Chiral Biomarkers in Meteorites

    NASA Technical Reports Server (NTRS)

    Hoover, Richard B.

    2010-01-01

    The chirality of organic molecules with the asymmetric location of group radicals was discovered in 1848 by Louis Pasteur during his investigations of the rotation of the plane of polarization of light by crystals of sodium ammonium paratartrate. It is well established that the amino acids in proteins are exclusively Levorotary (L-aminos) and the sugars in DNA and RNA are Dextrorotary (D-sugars). This phenomenon of homochirality of biological polymers is a fundamental property of all life known on Earth. Furthermore, abiotic production mechanisms typically yield recemic mixtures (i.e. equal amounts of the two enantiomers). When amino acids were first detected in carbonaceous meteorites, it was concluded that they were racemates. This conclusion was taken as evidence that they were extraterrestrial and produced by abiologically. Subsequent studies by numerous researchers have revealed that many of the amino acids in carbonaceous meteorites exhibit a significant L-excess. The observed chirality is much greater than that produced by any currently known abiotic processes (e.g. Linearly polarized light from neutron stars; Circularly polarized ultraviolet light from faint stars; optically active quartz powders; inclusion polymerization in clay minerals; Vester-Ulbricht hypothesis of parity violations, etc.). This paper compares the measured chirality detected in the amino acids of carbonaceous meteorites with the effect of these diverse abiotic processes. IT is concluded that the levels observed are inconsistent with post-arrival biological contamination or with any of the currently known abiotic production mechanisms. However, they are consistent with ancient biological processes on the meteorite parent body. This paper will consider these chiral biomarkers in view of the detection of possible microfossils found in the Orgueil and Murchison carbonaceous meteorites. Energy dispersive x-ray spectroscopy (EDS) data obtained on these morphological biomarkers will be

  2. Generalized simplicial chiral models

    NASA Astrophysics Data System (ADS)

    Alimohammadi, Masoud

    2000-02-01

    Using the auxiliary field representation of the simplicial chiral models on a ( d-1)-dimensional simplex, the simplicial chiral models are generalized through replacing the term Tr (AA †) in the Lagrangian of these models by an arbitrary class function of AA †; V(AA †) . This is the same method used in defining the generalized two-dimensional Yang-Mills theories (gYM 2) from ordinary YM 2. We call these models the "generalized simplicial chiral models". Using the results of the one-link integral over a U( N) matrix, the large- N saddle-point equations for eigenvalue density function ρ( z) in the weak ( β> βc) and strong ( β< βc) regions are computed. In d=2, where the model is in some sense related to the gYM 2 theory, the saddle-point equations are solved for ρ( z) in the two regions, and the explicit value of critical point βc is calculated for V(B)= Tr B n(B=AA †) . For V(B)= Tr B 2, Tr B 3, and Tr B4, the critical behaviour of the model at d=2 is studied, and by calculating the internal energy, it is shown that these models have a third order phase transition.

  3. Chiral magnetohydrodynamic turbulence

    NASA Astrophysics Data System (ADS)

    Pavlović, Petar; Leite, Natacha; Sigl, Günter

    2017-07-01

    In this work the influence of the chiral anomaly effect on the evolution of magnetohydrodynamic turbulence was studied. We argue that before the electroweak symmetry breaking and for temperatures high enough such that the electron mass can be ignored, the description of a charged plasma in general needs to take into account the interplay between turbulence and the anomaly effects. It was demonstrated that this generalization can have important consequences on the evolution of turbulence, leading to the creation of maximally-helical fields from initially nonhelical ones. Therefore, chiral effects can strongly support turbulent inverse cascade, and lead to a slower decrease of the magnetic field with time, and also to a faster growth of the correlation length, when compared to the evolution predicted by the standard magnetohydrodynamics description. Using the weak anomaly approximation, and treating the anomaly contributions to magnetic energy and helicity as a small perturbation, we derive the specific solutions for the inverse cascade regime that demonstrate how chiral effects support the inverse cascade.

  4. Collective Hamiltonian for chiral modes

    NASA Astrophysics Data System (ADS)

    Chen, Q. B.; Zhang, S. Q.; Zhao, P. W.; Jolos, R. V.; Meng, J.

    2013-02-01

    A collective model is proposed to describe the chiral rotation and vibration and applied to a system with one h11/2 proton particle and one h11/2 neutron hole coupled to a triaxial rigid rotor. The collective Hamiltonian is constructed from the potential energy and mass parameter obtained in the tilted axis cranking approach. By diagonalizing the collective Hamiltonian with a box boundary condition, it is found that for the chiral rotation, the partner states become more degenerate with the increase of the cranking frequency, and for the chiral vibrations, their important roles for the collective excitation are revealed at the beginning of the chiral rotation region.

  5. Microchip electrophoresis for chiral separations.

    PubMed

    Belder, Detlev; Ludwig, Martin

    2003-08-01

    Microchip electrophoresis (MCE) is a promising new technique for the separation of enantiomers. This recently introduced technique enables chiral separations to be performed in seconds on tiny micromachined devices. This review is intended to give a brief introduction into the principles of chiral separations with MCE with regard to methodology and instrumentation. Different approaches to realize chiral separations in microfluidic devices are described and discussed. This review gives an overview of original work done in this field with emphasis on approaches to improve detection and resolution in chiral MCE.

  6. Free-standing chiral plasmonics

    NASA Astrophysics Data System (ADS)

    Leong, Eunice Sok Ping; Deng, Jie; Wu, Siji; Khoo, Eng Huat; Liu, Yan Jun

    2014-11-01

    Chiral plasmonic nanostructures offer the ability to achieve strong optical circular dichroism (CD) activity over a broad spectral range, which has been challenging for chiral molecules. Chiral plasmonic nanostructures have been extensively studied based on top-down and bottom-up fabrication techniques. Particularly, in the top-down electron-beam lithography, 3D plasmonic nanostructure fabrication involves layer-by-layer patterning and complex alignment, which is time-consuming and causes many defects in the structures. Here, we present a free-standing 3D chiral plamonic nanostructures using the electron-beam lithography technique with much simplified fabrication processes. The 3D chiral plasmonic nanostructures consist of a free-standing ultrathin silicon nitride membrane with well-aligned L-shape metal nanostructures on one side and disk-shape ones on the other side. The free-standing membrane provides an ultra-smooth metal/dielectric interface and uniformly defines the gap between the upper and lower layers in an array of chiral nanostructures. Such free-standing chiral plasmonic nanostructures exhibit strong CD at optical frequencies, which can be engineered by simply changing the disk size on one side of the membrane. Experimental results are in good agreement with the finite-difference time-domain simulations. Such free-standing chiral plasmonics holds great potential for chirality analysis of biomolecules, drugs, and chemicals.

  7. Chiral drag force

    NASA Astrophysics Data System (ADS)

    Rajagopal, Krishna; Sadofyev, Andrey V.

    2015-10-01

    We provide a holographic evaluation of novel contributions to the drag force acting on a heavy quark moving through strongly interacting plasma. The new contributions are chiral in the sense that they act in opposite directions in plasmas containing an excess of left- or right-handed quarks. The new contributions are proportional to the coefficient of the axial anomaly, and in this sense also are chiral. These new contributions to the drag force act either parallel to or antiparallel to an external magnetic field or to the vorticity of the fluid plasma. In all these respects, these contributions to the drag force felt by a heavy quark are analogous to the chiral magnetic effect (CME) on light quarks. However, the new contribution to the drag force is independent of the electric charge of the heavy quark and is the same for heavy quarks and antiquarks, meaning that these novel effects do not in fact contribute to the CME current. We show that although the chiral drag force can be non-vanishing for heavy quarks that are at rest in the local fluid rest frame, it does vanish for heavy quarks that are at rest in a suitably chosen frame. In this frame, the heavy quark at rest sees counterpropagating momentum and charge currents, both proportional to the axial anomaly coefficient, but feels no drag force. This provides strong concrete evidence for the absence of dissipation in chiral transport, something that has been predicted previously via consideration of symmetries. Along the way to our principal results, we provide a general calculation of the corrections to the drag force due to the presence of gradients in the flowing fluid in the presence of a nonzero chemical potential. We close with a consequence of our result that is at least in principle observable in heavy ion collisions, namely an anticorrelation between the direction of the CME current for light quarks in a given event and the direction of the kick given to the momentum of all the heavy quarks and

  8. A stereoselective synthesis of (+)-physoperuvine using a tandem aza-Claisen rearrangement and ring closing metathesis reaction.

    PubMed

    Zaed, Ahmed M; Swift, Michael D; Sutherland, Andrew

    2009-07-07

    A stereoselective synthesis of (+)-physoperuvine, a tropane alkaloid from Physalis peruviana Linne has been developed using a one-pot tandem aza-Claisen rearrangement and ring closing metathesis reaction to form the key amino-substituted cycloheptene ring.

  9. Tuning PCP-Ir complexes: the impact of an N-heterocyclic olefin.

    PubMed

    Iglesias, Manuel; Iturmendi, Amaia; Sanz Miguel, Pablo J; Polo, Victor; Pérez-Torrente, Jesús J; Oro, Luis A

    2015-08-11

    A new PCP-type ligand based on an N-heterocyclic olefin (NHO) scaffold has been prepared. The flexibility of this ligand, which is able to adopt facial coordination modes in Ir(I) or meridional in Ir(III) complexes, can be attributed to the dual nature (ylide-olefin) of the NHO scaffold. This results in a rare case of olefin "slippage" that is supported by X-ray crystallography and DFT calculations.

  10. Nickel-Catalyzed Heck-Type Reactions of Benzyl Chlorides and Simple Olefins

    PubMed Central

    Matsubara, Ryosuke; Gutierrez, Alicia C.; Jamison, Timothy F.

    2011-01-01

    Nickel-catalyzed intermolecular benzylation and heterobenzylation of unactivated alkenes to provide functionalized allylbenzene derivatives is described. A wide range of both the benzyl chloride and alkene coupling partners are tolerated. In contrast to analogous palladium-catalyzed variants of this process, all reactions described herein employ electronically unbiased aliphatic olefins (including ethylene), proceed at room temperature and provide 1,1-disubstituted olefins over the more commonly observed 1,2-disubstituted olefins with very high selectivity. PMID:22066899

  11. Rare-earth-catalyzed C-H bond addition of pyridines to olefins.

    PubMed

    Guan, Bing-Tao; Hou, Zhaomin

    2011-11-16

    An efficient and general protocol for the ortho-alkylation of pyridines via C-H addition to olefins has been developed, using cationic half-sandwich rare-earth catalysts, which provides an atom-economical method for the synthesis of alkylated pyridine derivatives. A wide range of pyridine and olefin substrates including α-olefins, styrenes, and conjugated dienes are compatible with the catalysts.

  12. Isothermal Titration Calorimetry of Chiral Polymeric Nanoparticles.

    PubMed

    Werber, Liora; Preiss, Laura C; Landfester, Katharina; Muñoz-Espí, Rafael; Mastai, Yitzhak

    2015-09-01

    Chiral polymeric nanoparticles are of prime importance, mainly due to their enantioselective potential, for many applications such as catalysis and chiral separation in chromatography. In this article we report on the preparation of chiral polymeric nanoparticles by miniemulsion polymerization. In addition, we describe the use of isothermal titration calorimetry (ITC) to measure the chiral interactions and the energetics of the adsorption of enantiomers from aqueous solutions onto chiral polymeric nanoparticles. The characterization of chirality in nano-systems is a very challenging task; here, we demonstrate that ITC can be used to accurately determine the thermodynamic parameters associated with the chiral interactions of nanoparticles. The use of ITC to measure the energetics of chiral interactions and recognition at the surfaces of chiral nanoparticles can be applied to other nanoscale chiral systems and can provide further insight into the chiral discrimination processes of nanomaterials.

  13. The Ziegler—Natta olefin insertion reaction for cationic metals

    NASA Astrophysics Data System (ADS)

    Jensen, Vidar R.; Siegban, Per E. M.

    1993-09-01

    The catalytic Ziegler—Natta polymerization reaction has been studied for a set of metal cations, in order to identify the role of the positive charge on this process. Geometry optimizations have been performed for the reactant metal—methyl systems, the π-coordinated olefin systems, the transition states for the olefin insertion and finally for the product metal—propyl systems. All valence electrons are correlated. The cations selected for this study are the transition metals Zr + and Ti +, the non-transition metals Be +, Mg +, Al + and finally also Si +. The transition metal cations are found to have very low barriers for the insertion, but the lowest barrier is actually found for Be +. The results are discussed in terms of the ionization energies and the accessibility to valence p and d orbitals. Comparisons are made to previous theoretical work on cationic model systems.

  14. Flammability limits of olefinic and saturated fluoro-compounds.

    PubMed

    Kondo, Shigeo; Takizawa, Kenji; Takahashi, Akifumi; Tokuhashi, Kazuaki; Mizukado, Junji; Sekiya, Akira

    2009-11-15

    Flammability limits were measured for a number of olefinic and saturated fluoro-compounds in a 12l spherical glass vessel. The obtained data together with the ones of previous studies have been analyzed based on the F-number scheme of flammability limits. The flammability limits of these compounds have been found to be explained very well by the present scheme of interpretation. The flammability limits are dependent upon distribution of F atoms in a molecule as well as upon F-substitution rate itself. It has been found that -O-CF(3) group in a molecule conspicuously decreases the flammability of the compound, while -C-CF(3) group does not much. For olefinic compounds, distribution of F atoms around double bonds markedly diminishes the flammability of the molecule.

  15. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1991-01-01

    The objective of this project is to evaluate the efficacy of low severity coal liquefaction in the presence of highly reactive hydrogen donors, cyclic olefins. The work that was performed this quarter involved performing a literature search in which different aspects of low severity coal liquefaction were examined. In addition, two new mater's graduate students learned the fundamental differences between high severity coal liquefaction and low severity coal liquefaction by examining the literature and reading texts on coal liquefaction. The literature review presented for the first quarter's work is a compilation of the material which we have found to data involving low severity coal liquefaction. Additional review of low severity liquefaction literature is being conducted this quarter and will be reported in the next quarterly report. In addition, a summary of the work involving the reactivity of cyclic olefins in the absence and presence of coal will be presented next quarter.

  16. Syngas to olefins via dimethyl ether over zeolite catalysts

    SciTech Connect

    Lee, B.G.; Sardesai, A.; Lee, S.

    1998-12-31

    Coal or natural gas-based syngas can be converted to dimethyl ether (DME) in a dual catalytic, single-stage liquid phase process. The process described here converts dimethyl ether to lower olefins, such as ethylene, propylene, and butenes. Thus, a novel process of producing olefins from syngas via dimethyl ether has been introduced. The process feasibility of dimethyl ether conversion has been evaluated and the range of products of this process has also been identified. The effect of operating parameters and catalyst characteristics on product selectivity has been studied. The superior process advantages as well as its competitive economics quite clearly identify this process to be quite promising when conducted on an industrial scale.

  17. Cyclic olefins as new hydrogen donor compounds for coal liquefaction

    SciTech Connect

    Bedell, M.W.; Curtis, C.W. )

    1990-01-01

    A new set of hydrogen donor compounds, cyclic olefins (CLO), has been evaluated to determine their effectiveness as hydrogen donors to coal. These cyclic olefins are hydroaromatic species which do not contain aromatic rings. The efficacy of these donors has been compared to conventional hydroaromatics. The CLO's under study are 1,4,5,8-tetrahydronaphthalene, also known as isotetralin, and 1,4,5,8,9,10-hexahydroanthracene. In this paper, the thermal and catalytic reactivity of the CLO's under nitrogen and hydrogen at coal liquefaction temperature is discussed. Results for the reactions of the CLO's and their conventional hydroaromatic analogues, e.g. tetralin, 9,10-dihydroanthracene, and octahydroanthracene, with Western Kentucky No. 9 coal are discussed.

  18. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1991-01-01

    The objective of this project is to evaluate the efficacy of low severity coal liquefaction in the presence of highly reactive hydrogen donors, cyclic olefins. The work that was performed this quarter involved performing a literature search in which different aspects of low severity coal liquefaction were examined. In addition, two new master's graduate students learned the fundamental differences between high severity coal liquefaction and low severity coal liquefaction by examining the literature and reading texts on coal liquefaction. The literature review presented for the first quarter's work is a compilation of the material which we have found to date involving low severity coal liquefaction. Additional review of low severity liquefaction literature is being conducted this quarter and will be reported in the next quarterly report. In addition, a summary of the work involving the reactivity of cyclic olefins in the absence and presence of coal will be presented next quarter.

  19. Probing the Mechanism of the Double C—H (De)Activation Route of a Ru-Based Olefin Metathesis Catalyst

    NASA Astrophysics Data System (ADS)

    Poater, Albert; Cavallo, Luigi

    A theoretical study of a double C—H activation mechanism that deactivates a family of second generation Ru-based catalysts is presented. DFT calculations are used to rationalize the complex mechanistic pathway from the starting precatalyst to the experimentally characterized decomposition products. In particular, we show that all the intermediates proposed by Grubbs and coworkers are indeed possible intermediates in the deactivation pathway, although the sequence of steps is somewhat different

  20. Homogeneous catalysis with methane. A strategy for the hydromethylation of olefins based on the nondegenerate exchange of alkyl groups and sigma-bond metathesis at scandium.

    PubMed

    Sadow, Aaron D; Tilley, T Don

    2003-07-02

    The scandium alkyl Cp*(2)ScCH(2)CMe(3) (2) was synthesized by the addition of a pentane solution of LiCH(2)CMe(3) to Cp*(2)ScCl at low temperature. Compound 2 reacts with the C-H bonds of hydrocarbons including methane, benzene, and cyclopropane to yield the corresponding hydrocarbyl complex and CMe(4). Kinetic studies revealed that the metalation of methane proceeds exclusively via a second-order pathway described by the rate law: rate = k[2][CH(4)] (k = 4.1(3) x 10(-4) M(-1)s(-1) at 26 degrees C). The primary inter- and intramolecular kinetic isotope effects (k(H)/k(D) = 10.2 (CH(4) vs CD(4)) and k(H)/k(D) = 5.2(1) (CH(2)D(2)), respectively) are consistent with a linear transfer of hydrogen from methane to the neopentyl ligand in the transition state. Activation parameters indicate that the transformation involves a highly ordered transition state (DeltaS++ = -36(1) eu) and a modest enthalpic barrier (DeltaH++ = 11.4(1) kcal/mol). High selectivity toward methane activation suggested the participation of this chemistry in a catalytic hydromethylation, which was observed in the slow, Cp*(2)ScMe-catalyzed addition of methane across the double bond of propene to form isobutane.

  1. Improved light olefin yield from methyl bromide coupling over modified SAPO-34 molecular sieves.

    PubMed

    Zhang, Aihua; Sun, Shouli; Komon, Zachary J A; Osterwalder, Neil; Gadewar, Sagar; Stoimenov, Peter; Auerbach, Daniel J; Stucky, Galen D; McFarland, Eric W

    2011-02-21

    As an alternative to the partial oxidation of methane to synthesis gas followed by methanol synthesis and the subsequent generation of olefins, we have studied the production of light olefins (ethylene and propylene) from the reaction of methyl bromide over various modified microporous silico-aluminophosphate molecular-sieve catalysts with an emphasis on SAPO-34. Some comparisons of methyl halides and methanol as reaction intermediates in their conversion to olefins are presented. Increasing the ratio of Si/Al and incorporation of Co into the catalyst framework improved the methyl bromide yield of light olefins over that obtained using standard SAPO-34.

  2. Process for upgrading olefinic gasoline by etherification wherein asymmetrical dialkyl ethers are produced

    SciTech Connect

    Mizrahi, S.; Sorensen, C.M.; Tabak, S.A.

    1992-01-07

    This patent describes an integrated process for improving the value of an olefin-containing gasoline stream. It includes providing an olefinic gasoline feedstream containing C{sub 3}-C{sub 8} olefins; fractionating the olefinic gasoline feedstream to evolve a first stream enriched in C{sub 3}-C{sub 4} olefins and a second gasoline stream enriched in C{sub 5}-C{sub 8} olefins; converting at least 30% by weight of the C{sub 3}-C{sub 4} olefins contained in the first stream of step (b) in a hydration zone to a hydration zone effluent containing alcohols in an aqueous mixture comprising isopropyl alcohol and sec-butyl alcohol with C{sub 3}- C{sub 4} primary alcohols; fractionating the hydration zone effluent into a recycle stream rich in C{sub 3}-C{sub 4} olefins and a purified hydrate stream containing alcohols in an aqueous mixture comprising isopropyl alcohol and sec-butyl alcohol with C{sub 3}-C{sub 4} primary alcohols; extracting the alcohols from the purified hydrate stream with the olefin-enriched second gasoline stream.

  3. Vanadyl cationic complexes as catalysts in olefin oxidation.

    PubMed

    Nunes, Carla D; Vaz, Pedro D; Félix, Vítor; Veiros, Luis F; Moniz, Tânia; Rangel, Maria; Realista, Sara; Mourato, Ana C; Calhorda, Maria José

    2015-03-21

    Three new mononuclear oxovanadium(IV) complexes [VO(acac)(R-BIAN)]Cl (BIAN = 1,2-bis{(R-phenyl)imino}acenaphthene, R = H, 1; CH3, 2; Cl, 3) were prepared and characterized. They promoted the catalytic oxidation of olefins such as cyclohexene, cis-cyclooctene, and styrene with both tbhp (tert-butylhydroperoxide) and H2O2, and of enantiopure olefins (S(-)- and R(+)-pinene, and S(-)- and R(+)-limonene) selectively to their epoxides, with tbhp as the oxidant. The TOFs for styrene epoxidation promoted by complex 3 with H2O2 (290 mol mol(-1)V h(-1)) and for cis-cyclooctene epoxidation by 2 with tbhp (248 mol mol(-1)V h(-1)) are particularly good. Conversions reached 90% for several systems with tbhp, and were lower with H2O2. A preference for the internal C=C bond, rather than the terminal one, was found for limonene. Kinetic data indicate an associative process as the first step of the reaction and complex [VO(acac)(H-BIAN)](+) (1(+)) was isolated in an FTICR cell after adding tbhp to 1. EPR studies provide evidence for the presence of a V(IV) species in solution, until at least 48 hours after the addition of tbhp and cis-cyclooctene, and cyclic voltammetry studies revealed an oxidation potential above 1 V for complex 1. DFT calculations suggest that a [VO(H-BIAN)(MeOO)](+) complex is the likely active V(IV) species in the catalytic cycle from which two competitive mechanisms for the reaction proceed, an outer sphere path with an external attack of the olefin at the coordinated peroxide, and an inner sphere mechanism starting with a complex with the olefin coordinated to vanadium.

  4. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

    Koby, Lawrence; Ningappa, Jyothi B.; Dakesssian, Maria; Cuccia, Louis A.

    2005-01-01

    The optimal conditions for the crystallization of achiral ethylenediamine sulfate into large chiral crystals that are ideal for polarimetry studies and observation using Polaroid sheets are presented. This experiment is an ideal undergraduate experiment, which clearly demonstrates the chiral crystallization of an achiral molecule.

  5. Chiral Crystallization of Ethylenediamine Sulfate

    ERIC Educational Resources Information Center

    Koby, Lawrence; Ningappa, Jyothi B.; Dakesssian, Maria; Cuccia, Louis A.

    2005-01-01

    The optimal conditions for the crystallization of achiral ethylenediamine sulfate into large chiral crystals that are ideal for polarimetry studies and observation using Polaroid sheets are presented. This experiment is an ideal undergraduate experiment, which clearly demonstrates the chiral crystallization of an achiral molecule.

  6. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

  7. CHIRAL PESTICIDES: OCCURRENCE AND SIGNIFICANCE

    EPA Science Inventory

    Like amino acids, certain pesticides exist in "left-handed" and "right-handed" (chiral) forms. Commercially available chiral pesticides are produced as racemic mixtures in which the ratio of the two forms (or enantiomers) is 1:1. Enantiomers have the same ...

  8. Empirical description of chiral autocatalysis.

    PubMed

    Micskei, Karoly; Póta, György; Caglioti, Luciano; Palyi, Gyula

    2006-05-11

    The only known example of chiral autocatalysis is the alkylation of N-heterocyclic aldehydes with iPr(2)Zn (Soai reaction). The mechanism and some details of this reaction are not yet clear. An empirical formula is proposed here for the description of this chiral autocatalytic reaction. This formula allows the calculation of some very informative parameters.

  9. Integrated process and dual-function catalyst for olefin epoxidation

    DOEpatents

    Zhou, Bing; Rueter, Michael

    2003-01-01

    The invention discloses a dual-functional catalyst composition and an integrated process for production of olefin epoxides including propylene oxide by catalytic reaction of hydrogen peroxide from hydrogen and oxygen with olefin feeds such as propylene. The epoxides and hydrogen peroxide are preferably produced simultaneously in situ. The dual-functional catalyst comprises noble metal crystallites with dimensions on the nanometer scale (on the order of <1 nm to 10 nm), specially dispersed on titanium silicalite substrate particles. The dual functional catalyst catalyzes both the direct reaction of hydrogen and oxygen to generate hydrogen peroxide intermediate on the noble metal catalyst surface and the reaction of the hydrogen peroxide intermediate with the propylene feed to generate propylene oxide product. Combining both these functions in a single catalyst provides a very efficient integrated process operable below the flammability limits of hydrogen and highly selective for the production of hydrogen peroxide to produce olefin oxides such as propylene oxide without formation of undesired co-products.

  10. Synthesis of polytetrafluoroethylene based olefinic copolymer by gamma radiation grafting

    NASA Astrophysics Data System (ADS)

    Ferreto, H. F. R.; Lima, L. F. C. P.; Parra, D. F.; Zaia, V.; Lugão, A. B.

    2007-12-01

    High speed extrusion of linear low density polyethylene (LLDPE) is limited by processes shortcoming known as 'melt fracture' and 'sharkskin', which are surface defect of the extruded polymer. This defect results in a product with a rough surface that lacks luster and with poor surface properties. The fluoropolymer processing additives are used to eliminate the surface defect by coating the die wall and inducing slip at the coated fluoropolymer surface/LLDPE interface. The aim of this study was to obtain a recycled polytetrafluoroethylene polymer grafted with an olefin that could improve the extrudability of the LLDPE. The copolymer was obtained by irradiating recycled PTFE in an inert atmosphere followed by grafting an olefinic monomer the polymeric matrix (PTFE). After a certain time of contact, the copolymer was heat treated to allow recombination and elimination of the radicals, both in a reactive and/or inert atmosphere. The olefinic monomer used was 1,3-butadiene. The 1,3-butadiene monomer was found to be more effective with respect to grafting. The specimens were studied using Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential thermogravimetry (DTG). The obtained copolymer (0.2-2.0 wt%) was mixed with LLDPE. The rheological properties of the mixture were determined with a torque rheometer. The results indicated that the developed process rendered a copolymer which when added to LLDPE, improved the extrusion process and eliminated the defect 'melt fracture'.

  11. 'Carbene radicals' in Co(II)(por)-catalyzed olefin cyclopropanation.

    PubMed

    Dzik, Wojciech I; Xu, Xue; Zhang, X Peter; Reek, Joost N H; de Bruin, Bas

    2010-08-11

    The mechanism of cobalt(II)-porphyrin-mediated cyclopropanation of olefins with diazoesters was studied. The first step--reaction of cobalt(II)-porphyrin with ethyl diazoacetate (EDA)--was examined using EPR and ESI-MS techniques. EDA reacts with cobalt(II)-porphyrin to form a 1:1 Co(por)(CHCOOEt) adduct that exists as two isomers: the 'bridging carbene' C' in which the 'carbene' is bound to the metal and the pyrrolic nitrogen of the porphyrin that has a d(7) configuration on the metal, and the 'terminal carbene' C in which the 'carbene' behaves as a redox noninnocent ligand having a d(6) cobalt center and the unpaired electron residing on the 'carbene' carbon atom. The subsequent reactivities of the thus formed 'cobalt carbene radical' with propene, styrene, and methyl acrylate were studied using DFT calculations. The calculations suggest that the formation of the carbene is the rate-limiting step for the unfunctionalized Co(II)(por) and that the cyclopropane ring formation proceeds via a stepwise radical process: Radical addition of the 'carbene radical' C to the C=C double bonds of the olefins results in formation of the gamma-alkyl radical intermediates D. Species D then easily collapse in almost barrierless ring-closure reactions (TS3) to form the cyclopropanes. This radical mechanism readily explains the high activity of Co(II)(por) species in the cyclopropanation of electron-deficient olefins such as methyl acrylate.

  12. Low severity coal liquefaction promoted by cyclic olefins

    SciTech Connect

    Curtis, C.W.

    1992-07-27

    Low severity coal liquefaction allows for solubilization of coal with reduced gas make. These lower severity conditions may result in some selective bond rupture. Promotion of coal solubilization through hydrogen transfer using highly active and effective hydrogen donors is the objective of this study. The highly effective donors being tested are cyclic olefins. Representative cyclic olefins are isotetralin, which is 1,4,5,8-tetrahydronaphthalene, and 1,4,5,8,9,10-hexahydroanthracene. These compounds are hydroaromatics without aromatic rings and have been shown to be highly effective donors. The objective of the work performed in this study during this quarter was to evaluate reaction parameters for low severity liquefaction reactions using the cyclic olefin, hexahydroanthracene, and the aromatic, anthracene. These model compounds were reacted under a variety of conditions to evaluate their reactivity without coal. The reactions were performed under both thermal and catalytic conditions. Finely divided catalysts from different molybdenum precursors were used to determine their activity in promoting hydrogenation and hydrogen transfer at low severity conditions. The catalysts used were Molyvan L, sulfurized oxymolybdenum dithiocarbamate, molybdenum naphthenate, and Molyvan 822, organo molybdenum dithiocarbamate.

  13. Mass-Selective Chiral Analysis

    NASA Astrophysics Data System (ADS)

    Boesl, Ulrich; Kartouzian, Aras

    2016-06-01

    Three ways of realizing mass-selective chiral analysis are reviewed. The first is based on the formation of diastereomers that are of homo- and hetero- type with respect to the enantiomers of involved chiral molecules. This way is quite well-established with numerous applications. The other two ways are more recent developments, both based on circular dichroism (CD). In one, conventional or nonlinear electronic CD is linked to mass spectrometry (MS) by resonance-enhanced multiphoton ionization. The other is based on CD in the angular distribution of photoelectrons, which is measured in combination with MS via photoion photoelectron coincidence. Among the many important applications of mass-selective chiral analysis, this review focuses on its use as an analytical tool for the development of heterogeneous enantioselective chemical catalysis. There exist other approaches to combine chiral analysis and mass-selective detection, such as chiral chromatography MS, which are not discussed here.

  14. Quark structure of chiral solitons

    SciTech Connect

    Dmitri Diakonov

    2004-05-01

    There is a prejudice that the chiral soliton model of baryons is something orthogonal to the good old constituent quark models. In fact, it is the opposite: the spontaneous chiral symmetry breaking in strong interactions explains the appearance of massive constituent quarks of small size thus justifying the constituent quark models, in the first place. Chiral symmetry ensures that constituent quarks interact very strongly with the pseudoscalar fields. The ''chiral soliton'' is another word for the chiral field binding constituent quarks. We show how the old SU(6) quark wave functions follow from the ''soliton'', however, with computable relativistic corrections and additional quark-antiquark pairs. We also find the 5-quark wave function of the exotic baryon Theta+.

  15. Controlling Chirality of Entropic Crystals.

    PubMed

    Damasceno, Pablo F; Karas, Andrew S; Schultz, Benjamin A; Engel, Michael; Glotzer, Sharon C

    2015-10-09

    Colloidal crystal structures with complexity and diversity rivaling atomic and molecular crystals have been predicted and obtained for hard particles by entropy maximization. However, thus far homochiral colloidal crystals, which are candidates for photonic metamaterials, are absent. Using Monte Carlo simulations we show that chiral polyhedra exhibiting weak directional entropic forces self-assemble either an achiral crystal or a chiral crystal with limited control over the crystal handedness. Building blocks with stronger faceting exhibit higher selectivity and assemble a chiral crystal with handedness uniquely determined by the particle chirality. Tuning the strength of directional entropic forces by means of particle rounding or the use of depletants allows for reconfiguration between achiral and homochiral crystals. We rationalize our findings by quantifying the chirality strength of each particle, both from particle geometry and potential of mean force and torque diagrams.

  16. Chiral models: Geometrical aspects

    NASA Astrophysics Data System (ADS)

    Perelomov, A. M.

    1987-02-01

    Two-dimensional classical chiral models of field theory are considered, the main attention being paid on geometrical aspects of such theories. A characteristic feature of these models is that the interaction is inserted not by adding the interaction Lagrangian to the free field Lagrangian, but has a purely geometrical origin and is related to the inner curvature of the manifold. These models are in many respects analogous to non-Abelian gauge theories and as became clear recently, they are also important for the superstring theory which nowadays is the most probable candidate for a truly unified theory of all interactions including gravitation.

  17. Observation of different catalytic activity of various 1-olefins during ethylene/1-olefin copolymerization with homogeneous metallocene catalysts.

    PubMed

    Wannaborworn, Mingkwan; Praserthdam, Piyasan; Jongsomjit, Bunjerd

    2011-01-07

    This research aimed to investigate the copolymerization of ethylene and various 1-olefins. The comonomer lengths were varied from 1-hexene (1-C₆) up to 1-octadecene (1-C₁₈) in order to study the effect of comonomer chain length on the activity and properties of the polymer in the metallocene/MAO catalyst system. The results indicated that two distinct cases can be described for the effect of 1-olefin chain length on the activity. Considering the short chain length comonomers, such as 1-hexene, 1-octene and 1-decene, it is obvious that the polymerization activity decreased when the length of comonomer was higher, which is probably due to increased steric hindrance at the catalytic center hindering the insertion of ethylene monomer to the active sites, hence, the polymerization rate decreased. On the contrary, for the longer chain 1-olefins, namely 1-dodecene, 1-tetradecene and 1-octadecene, an increase in the comonomer chain length resulted in better activity due to the opening of the gap aperture between C(p)(centroid)-M-C(p)-(centroid), which forced the coordination site to open more. This effect facilitated the polymerization of the ethylene monomer at the catalytic sites, and thus, the activity increased. The copolymers obtained were further characterized using thermal analysis, X-ray diffraction spectroscopy and ¹³C-NMR techniques. It could be seen that the melting temperature and comonomer distribution were not affected by the 1-olefin chain length. The polymer crystallinity decreased slightly with increasing comonomer chain length. Moreover, all the synthesized polymers were typical LLDPE having random comonomer distribution.

  18. Extended surface chirality from supramolecular assemblies of adsorbed chiral molecules

    NASA Astrophysics Data System (ADS)

    Ortega Lorenzo, M.; Baddeley, C. J.; Muryn, C.; Raval, R.

    2000-03-01

    The increasing demand of the chemical and pharmaceutical industries for enantiomerically pure compounds has spurred the development of a range of so-called `chiral technologies' (ref. 1), which aim to exert the ultimate control over a chemical reaction by directing its enantioselectivity. Heterogeneous enantioselective catalysis is particularly attractive because it allows the production and ready separation of large quantities of chiral product while using only small quantities of catalyst. Heterogeneous enantioselectivity is usually induced by adsorbing chiral molecules onto catalytically active surfaces. A mimic of one such catalyst is formed by adsorbing (R,R)-tartaric acid molecules on Cu(110) surfaces: this generates a variety of surface phases, of which only one is potentially catalytically active, and leaves the question of how adsorbed chiral molecules give rise to enantioselectivity. Here we show that the active phase consists of extended supramolecular assemblies of adsorbed (R,R)-tartaric acid, which destroy existing symmetry elements of the underlying metal and directly bestow chirality to the modified surface. The adsorbed assemblies create chiral `channels' exposing bare metal atoms, and it is these chiral spaces that we believe to be responsible for imparting enantioselectivity, by forcing the orientation of reactant molecules docking onto catalytically active metal sites. Our findings demonstrate that it is possible to sustain a single chiral domain across an extended surface-provided that reflection domains of opposite handedness are removed by a rigid and chiral local adsorption geometry, and that inequivalent rotation domains are removed by successful matching of the rotational symmetry of the adsorbed molecule with that of the underlying metal surface.

  19. Nanoscale chirality in metal and semiconductor nanoparticles.

    PubMed

    Kumar, Jatish; Thomas, K George; Liz-Marzán, Luis M

    2016-10-18

    The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided.

  20. Nanoscale chirality in metal and semiconductor nanoparticles

    PubMed Central

    Thomas, K. George

    2016-01-01

    The field of chirality has recently seen a rejuvenation due to the observation of chirality in inorganic nanomaterials. The advancements in understanding the origin of nanoscale chirality and the potential applications of chiroptical nanomaterials in the areas of optics, catalysis and biosensing, among others, have opened up new avenues toward new concepts and design of novel materials. In this article, we review the concept of nanoscale chirality in metal nanoclusters and semiconductor quantum dots, then focus on recent experimental and theoretical advances in chiral metal nanoparticles and plasmonic chirality. Selected examples of potential applications and an outlook on the research on chiral nanomaterials are additionally provided. PMID:27752651

  1. From chiral vibration to static chirality in ^135Nd

    NASA Astrophysics Data System (ADS)

    Mukhopadhyay, S.; Almehed, D.; Garg, U.; Frauendorf, S.; Li, T.; Madhusudhana Rao, P. V.; Wang, X.; Ghugre, S. S.; Carpenter, M. P.; Gros, S.; Hecht, A.; Janssens, R. V. F.; Kondev, F. G.; Lauritsen, T.; Seweryniak, D.; Zhu, S.

    2007-10-01

    Lifetimes were obtained in a DSAM measurement at Gammasphere, using the ^100Mo(^40Ar, 5n)^135Nd reaction. Electromagnetic transition probabilities have been measured for the intra- and inter-band transitions in the two sequences in the nucleus ^135Nd that were previously identified as a composite chiral bands [1]. The measurements are in good agreement with results of a new combination of TAC and RPA calculations. The chiral character of the bands is affirmed and it is observed that their behavior is associated with a transition from a vibrational into a static chiral regime. [1] S. Zhu et al., Phys. Rev. Lett.91, 132501 (2003).

  2. Chiral limit of QCD

    SciTech Connect

    Gupta, R.

    1994-12-31

    This talk contains an analysis of quenched chiral perturbation theory and its consequences. The chiral behavior of a number of quantities such as the pion mass m{sub pi}{sup 2}, the Bernard-Golterman ratios R and {sub X}, the masses of nucleons, and the kaon B-parameter are examined to see if the singular terms induced by the additional Goldstone boson, {eta}{prime}, are visible in present data. The overall conclusion (different from that presented at the lattice meeting) of this analysis is that even though there are some caveats attached to the indications of the extra terms induced by {eta}{prime} loops, the standard expressions break down when extrapolating the quenched data with m{sub q} < m{sub s}/2 to physical light quarks. I then show that due to the single and double poles in the quenched {eta}{prime}, the axial charge of the proton cannot be calculated using the Adler-Bell-Jackiw anomaly condition. I conclude with a review of the status of the calculation of light quark masses from lattice QCD.

  3. Chiral quantum optics

    NASA Astrophysics Data System (ADS)

    Lodahl, Peter; Mahmoodian, Sahand; Stobbe, Søren; Rauschenbeutel, Arno; Schneeweiss, Philipp; Volz, Jürgen; Pichler, Hannes; Zoller, Peter

    2017-01-01

    Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

  4. Chiral Conjugated Corrals.

    PubMed

    Ball, Melissa; Fowler, Brandon; Li, Panpan; Joyce, Leo A; Li, Fang; Liu, Taifeng; Paley, Daniel; Zhong, Yu; Li, Hexing; Xiao, Shengxiong; Ng, Fay; Steigerwald, Michael L; Nuckolls, Colin

    2015-08-12

    We present here a new design motif for strained, conjugated macrocycles that incorporates two different aromatics into the cycle with an -A-B-A-B- pattern. In this study, we demonstrate the concept by alternating electron donors and acceptors in a conjugated cycle. The donor is a bithiophene, and the acceptor is a perylene diimide derivative. The macrocycle formed has a persistent elliptiform cavity that is lined with the sulfur atoms of the thiophenes and the π-faces of the perylene diimide. Due to the linkage of the perylene diimide subunits, the macrocycles exist in both chiral and achiral forms. We separate the three stereoisomers using chiral high-performance liquid chromatography and study their interconversion. The mechanism for interconversion involves an "intramolecular somersault" in which one of the PDIs rotates around its transverse axis, thereby moving one of its diimide heads through the plane of the cavity. These unusual macrocycles are black in color with an absorption spectrum that spans the visible range. Density functional theory calculations reveal a photoinduced electron transfer from the bithiophene to the perylene diimide.

  5. The hierarchy of chirality.

    PubMed

    Schulgasser, Kalman; Witztum, Allan

    2004-09-21

    Twisting is a prevalent feature of long, thin vertical leaves; it has been shown that this twist contributes to the mechanical integrity of the leaf. We address the question as to how this twist comes about, and posit that it is a reflection of twist at a lower structural (geometric) level. The stiffness required for maintaining verticality in leaves is due to turgescent parenchyma cells, sometimes thickened epidermis, cuticle, and is generally most significantly contributed to by vascular bundles and fibers. These contain cellulose in the cell walls. Such cellulose chains spiral upward within the cell wall layers which are of a characteristic handedness. This results in an isolated cell behaving mechanically in a chiral manner; specifically elongation (contraction) of a single cell will result in rotation of the cell about its axis of particular handedness. We propose a mathematical model that shows that when cells are mechanically associated in groups, the chiral behavior of the cell will be expressed at larger scales, albeit to a mitigated degree. Thus cell extension during leaf development may explain the characteristic twist of such leaves.

  6. Chiral quantum optics.

    PubMed

    Lodahl, Peter; Mahmoodian, Sahand; Stobbe, Søren; Rauschenbeutel, Arno; Schneeweiss, Philipp; Volz, Jürgen; Pichler, Hannes; Zoller, Peter

    2017-01-25

    Advanced photonic nanostructures are currently revolutionizing the optics and photonics that underpin applications ranging from light technology to quantum-information processing. The strong light confinement in these structures can lock the local polarization of the light to its propagation direction, leading to propagation-direction-dependent emission, scattering and absorption of photons by quantum emitters. The possibility of such a propagation-direction-dependent, or chiral, light-matter interaction is not accounted for in standard quantum optics and its recent discovery brought about the research field of chiral quantum optics. The latter offers fundamentally new functionalities and applications: it enables the assembly of non-reciprocal single-photon devices that can be operated in a quantum superposition of two or more of their operational states and the realization of deterministic spin-photon interfaces. Moreover, engineered directional photonic reservoirs could lead to the development of complex quantum networks that, for example, could simulate novel classes of quantum many-body systems.

  7. Chiral perturbation theory with nucleons

    SciTech Connect

    Meissner, U.G.

    1991-09-01

    I review the constraints posed on the interactions of pions, nucleons and photons by the spontaneously broken chiral symmetry of QCD. The framework to perform these calculations, chiral perturbation theory, is briefly discussed in the meson sector. The method is a simultaneous expansion of the Greens functions in powers of external moments and quark masses around the massless case, the chiral limit. To perform this expansion, use is made of a phenomenological Lagrangian which encodes the Ward-identities and pertinent symmetries of QCD. The concept of chiral power counting is introduced. The main part of the lectures of consists in describing how to include baryons (nucleons) and how the chiral structure is modified by the fact that the nucleon mass in the chiral limit does not vanish. Particular emphasis is put on working out applications to show the strengths and limitations of the methods. Some processes which are discussed are threshold photopion production, low-energy compton scattering off nucleons, {pi}N scattering and the {sigma}-term. The implications of the broken chiral symmetry on the nuclear forces are briefly described. An alternative approach, in which the baryons are treated as very heavy fields, is touched upon.

  8. Chiral quantum dot based materials

    NASA Astrophysics Data System (ADS)

    Govan, Joseph; Loudon, Alexander; Baranov, Alexander V.; Fedorov, Anatoly V.; Gun'ko, Yurii

    2014-05-01

    Recently, the use of stereospecific chiral stabilising molecules has also opened another avenue of interest in the area of quantum dot (QD) research. The main goal of our research is to develop new types of technologically important quantum dot materials containing chiral defects, study their properties and explore their applications. The utilisation of chiral penicillamine stabilisers allowed the preparation of new water soluble white emitting CdS quantum nanostructures which demonstrated circular dichroism in the band-edge region of the spectrum. It was also demonstrated that all three types of QDs (D-, L-, and Rac penicillamine stabilised) show very broad emission bands between 400 and 700 nm due to defects or trap states on the surfaces of the nanocrystals. In this work the chiral CdS based quantum nanostructures have also been doped by copper metal ions and new chiral penicilamine stabilized CuS nanoparticles have been prepared and investigated. It was found that copper doping had a strong effect at low levels in the synthesis of chiral CdS nanostructures. We expect that this research will open new horizons in the chemistry of chiral nanomaterials and their application in biotechnology, sensing and asymmetric synthesis.

  9. [A comment on chiral thin layer chromatography].

    PubMed

    Chen, Xuexian; Yuan, Liming

    2016-01-01

    In recent eight years, authors' group has repeated a lot of experiments of chiral thin layer chromatography coming from literature. From the practical opinion, we summarized that there are nine characteristics for chiral thin layer chromatography. Some progresses of chiral thin layer chromatography are reviewed, and the enantioselectivity of a commercial chiral thin layer plate is introduced. The study of vancomycin as the chiral selector in thin layer chromatography is also reported.

  10. Solution-Phase Dynamic Assembly of Permanently Interlocked Aryleneethynylene Cages through Alkyne Metathesis

    SciTech Connect

    Wang, Qi; Yu, Chao; Long, Hai; Du, Ya; Jin, Yinghua; Zhang, Wei

    2015-05-08

    Highly stable permanently interlocked aryleneethynylene molecular cages were synthesized from simple triyne monomers using dynamic alkyne metathesis. The interlocked complexes are predominantly formed in the reaction solution in the absence of any recognition motif and were isolated in a pure form using column chromatography. This study is the first example of the thermodynamically controlled solution-phase synthesis of interlocked organic cages with high stability.

  11. Synthesis by Ring-Closing Metathesis and Cytotoxic Evaluation of Novel Thienylmacrolactones

    PubMed Central

    Krauss, Jürgen; Köbler, Daniela; Miller, Verena; Bracher, Franz

    2012-01-01

    This paper describes the synthesis and biological evaluation of macrolactones containing a thienyl substituent as simple analogues of epothilones. The compounds were prepared in a brief and efficient manner from thiophene-2-carbaldehyde using a ring-closing metathesis with Grubbs I or Grubbs II catalyst as the key step. The target lactones showed only insignificant cytotoxicity, while an intermediate simple thienyl carbinol showed very promising cytotoxicity. PMID:22396902

  12. Nitrene Metathesis and Catalytic Nitrene Transfer Promoted by Niobium Bis(imido) Complexes.

    PubMed

    Kriegel, Benjamin M; Bergman, Robert G; Arnold, John

    2016-01-13

    We report a metathesis reaction in which a nitrene fragment from an isocyanide ligand is exchanged with a nitrene fragment of an imido ligand in a series of niobium bis(imido) complexes. One of these bis(imido) complexes also promotes nitrene transfer to catalytically generate asymmetric dialkylcarbodiimides from azides and isocyanides in a process involving the Nb(V)/Nb(III) redox couple.

  13. Rapid assembly of structurally defined and highly functionalized conjugated dienes via tethered enyne metathesis.

    PubMed

    Yao, Q

    2001-06-28

    [reaction: see text] Conjugated dienes are versatile building blocks in organic synthesis, and the development of new methods for their synthesis remains an important topic in modern synthetic organic chemistry. We describe here an expedient synthesis of highly functionalized conjugated dienes through sequential silicon-tethered ring-closing enyne metathesis mediated by Grubbs' Ru carbene catalysts and Tamao oxidation. Notable attributes of this methodology include short synthetic manipulations and the structural complexity it confers on the resulting diene moiety.

  14. Epitaxial Electrodeposition of Chiral Metal Oxide Films

    NASA Astrophysics Data System (ADS)

    Switzer, Jay

    2006-03-01

    Chirality is ubiquitous in Nature. One enantiomer of a molecule is often physiologically active, while the other enantiomer may be either inactive or toxic. Chiral surfaces offer the possibility of developing heterogeneous enantiospecific catalysts that can more readily be separated from the products and reused. Chiral surfaces might also serve as electrochemical sensors for chiral molecules- perhaps even implantable chiral sensors that could be used to monitor drug levels in the body. Our trick to produce chiral surfaces is to electrodeposit low symmetry metal oxide films with chiral orientations on achiral substrates (see, Nature 425, 490, 2003). The relationship between three-dimensional and two-dimensional chirality will be discussed. Chiral surfaces lack mirror or glide plane symmetry. It is possible to produce chiral surfaces of materials which do not crystallize in chiral space groups. We have deposited chiral orientations of achiral CuO onto single-crystal Au and Cu using both tartaric acid and the amino acids alanine and valine to control the handedness of the electrodeposited films. We will present results on the chiral recognition of molecules such as tartaric or malic acid and L-dopa on the chiral electrodeposited CuO. Initial work on the electrochemical biomineralization of chiral nanostructures of calcite will also be discussed.

  15. Redox-Neutral Rh(III)-Catalyzed Olefination of Carboxamides with Trifluoromethyl Allylic Carbonate.

    PubMed

    Park, Jihye; Han, Sangil; Jeon, Mijin; Mishra, Neeraj Kumar; Lee, Seok-Yong; Lee, Jong Suk; Kwak, Jong Hwan; Um, Sung Hee; Kim, In Su

    2016-11-18

    The rhodium(III)-catalyzed olefination of various carboxamides with α-CF3-substituted allylic carbonate is described. This reaction provides direct access to linear CF3-allyl frameworks with complete trans-selectivity. In particular, a rhodium catalyst provided Heck-type γ-CF3-allylation products via the β-O-elimination of rhodacycle intermediate and subsequent olefin migration process.

  16. Beyond ketonization: selective conversion of carboxylic acids to olefins over balanced Lewis acid-base pairs.

    PubMed

    Baylon, Rebecca A L; Sun, Junming; Martin, Kevin J; Venkitasubramanian, Padmesh; Wang, Yong

    2016-04-11

    We report the direct conversion of mixed carboxylic acids to C-C olefins with up to 60 mol% carbon yield through cascade (cross) ketonization, (cross) aldolization and self-deoxygenation reactions. Co-feeding hydrogen provides an additional ketone hydrogenation/dehydration pathway to a wider range of olefins.

  17. A unique palladium catalyst for efficient and selective alkoxycarbonylation of olefins with formates.

    PubMed

    Fleischer, Ivana; Jennerjahn, Reiko; Cozzula, Daniela; Jackstell, Ralf; Franke, Robert; Beller, Matthias

    2013-03-01

    Forget about CO! Carbonylations are among the most important homogeneously catalyzed reactions in the chemical industry, but typically require carbon monoxide. Instead, straightforward and efficient alkoxycarbonylations of olefins can proceed with alkyl formates in the presence of a specific palladium catalyst. Aromatic, terminal aliphatic, and internal olefins are carbonylated to give industrially important linear esters at low catalyst loadings.

  18. High-valent iron-mediated cis-hydroxyacetoxylation of olefins.

    PubMed

    Mas-Balleste, Ruben; Fujita, Megumi; Que, Lawrence

    2008-04-14

    Evidence is obtained for the unprecedented cis-1,2-hydroxy-acetoxylation of olefins as minor products of the epoxidation of olefins by H2O2 that is catalyzed by nonheme iron complexes in the presence of acetic acid, providing further support for the previously proposed [(TPA)FeV(O)(OAc)]2+ oxidant.

  19. STIR: Redox-Switchable Olefin Polymerization Catalysis: Electronically Tunable Ligands for Controlled Polymer Synthesis

    DTIC Science & Technology

    2013-03-28

    REPORT Final Report: STIR: Redox-Switchable Olefin Polymerization Catalysis : Electronically Tunable Ligands for Controlled Polymer Synthesis 14...2211 15. SUBJECT TERMS Catalysis , Redox-Switchable, Polymerization, Polyolefins Brian K. Long University of Tennessee at Knoxville Office of Research...Polymerization Catalysis : Electronically Tunable Ligands for Controlled Polymer Synthesis Report Title ABSTRACT Olefin polymerization catalysts containing

  20. Catalytic Transformation of Bio-oil to Olefins with Molecular Sieve Catalysts

    NASA Astrophysics Data System (ADS)

    Huang, Wei-wei; Gong, Fei-yan; Zhai, Qi; Li, Quan-xin

    2012-08-01

    Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order: HZSM-5>SAPO-34>MCM-41> Y-zeolite. The highest olefins yield from bio-oil using HZSM-5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.