1 Phosphines and Related Tervalent Phosphorus Systems
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Mechanistic Insights Into the Hydrocyanation Reaction
Mechanistic insights into the hydrocyanation reaction Citation for published version (APA): Bini, L. (2009). Mechanistic insights into the hydrocyanation reaction. Technische Universiteit Eindhoven. https://doi.org/10.6100/IR644067 DOI: 10.6100/IR644067 Document status and date: Published: 01/01/2009 Document Version: Publisher’s PDF, also known as Version of Record (includes final page, issue and volume numbers) Please check the document version of this publication: • A submitted manuscript is the version of the article upon submission and before peer-review. There can be important differences between the submitted version and the official published version of record. People interested in the research are advised to contact the author for the final version of the publication, or visit the DOI to the publisher's website. • The final author version and the galley proof are versions of the publication after peer review. • The final published version features the final layout of the paper including the volume, issue and page numbers. Link to publication General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. • Users may download and print one copy of any publication from the public portal for the purpose of private study or research. • You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal. -
Design and Synthesis of Chiral Ligands and Their Applications in Transition
The Pennsylvania State University The Graduate School Department of Chemistry DESIGN AND SYNTHESIS OF CHIRAL LIGANDS AND THEIR APPLICATIONS IN TRANSITION METAL-CATALYZED ASYMMETRIC REACTIONS A Dissertation in Chemistry by Wei Li 2012 Wei Li Submitted in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2012 The dissertation of Wei Li was reviewed and approved* by the following: Gong Chen Assistant Professor of Chemistry Dissertation Advisor Chair of Committee Tom Mallouk Evan Pugh Professor of Material Chemistry and Physics Alex Radosevich Assistant Professor of Chemistry Qing Wang Associate Professor of Material Science and Engineering Xumu Zhang Professor of Chemistry Special Member Barbara J. Garrison Shapiro Professor of Chemistry Head of the Department of Chemistry *Signatures are on file in the Graduate School iii ABSTRACT Transition metal catalyzed reactions are among the most powerful and direct approaches for the synthesis of organic molecules. During the past several decades, phosphorous-containing ligands have been extensively studied in transition metal - catalyzed transformations particularly asymmetric hydrogenations. Development of new chiral ligands and efficient catalyst systems for various prochiral unsaturated substrates in asymmetric hydrogenations are the focus of this dissertation. An important family of atropisomeric biaryl bisphosphine ligands, C3*-TunePhos and related bisaminophosphines have been designed and synthesized. The Ru catalysts of the highly modular C3*-TunePhos have been proved to be highly efficient (up to 99.8% ee, up to 1,000,000 TON) for practical asymmetric hydrogenations of a wide range of unfunctionalized ketones as well as α-, β- keto esters and N-2-substituted allylphthalimides. The synthetic utility of bisaminophosphine ligands was studied for rhodium-catalyzed asymmetric hydrogenations of α-dehydroamino acid esters, affording up to 98% ee’s. -
Synthesis of C2-Symmetric P-Chiral Bis(Phosphine Borane)
Synthesis of C2-symmetric P-chiral bis(phosphine borane)s and their application in rhodium(I) catalyzed asymmetric transformation by Holly Ann Heath A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Montana State University © Copyright by Holly Ann Heath (2001) Abstract: A new development for the synthesis C2-Synnnetric P-Chiral Bis(phosphine borane) ligands is reported, These ligands are based on the asymmetric induction of prochiral phosphine ligands with organolithium/chiral diamine complexes. These ligands have been evaluated in asymmetric rhodium(I) catalyzed hydrogenation and [4 + 2] cycloisomerization reactions. Enantiomeric excesses as high as 99% were obtained for ene-diene cycloadditions. Synthesis of C2-Symmetric P-Chiral Bis(phosphine borane)s and Their Application in Rhodium(I) Catalyzed Asymmetric Transformation by Holly Ann Heath A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Chemistry Montana State University Bozeman, Montana March 2001 ii APPROVAL of a dissertation submitted by Holly Ann Heath This dissertation has been read by each member of the dissertation committee and has been found to be satisfactory regarding content, English usage, format, citations, bibliographic style, and consistency, and is ready for submission to the College of Graduate Studies. Dr. Thomas Livinghouse < Chairperson, Graduate Committee Date Approved for the Department of Chemistry Dr. Paul A. Grieco Department Head Approved for the College of Graduate Studies Dr. Bruce R. McLeod Graduate Dean Date iii STATEMENT OF PERMISSION TO USE In presenting this dissertation .in partial fulfillment of the requirements for a doctoral degree at Montana State University-Bozeman, I agree that the Library shall make it available to borrowers under rules of the Library. -
Studies of a Dirhodium Tetraphosphine Catalyst for Hydroformylation And
Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2012 Studies of a dirhodium tetraphosphine catalyst for hydroformylation and aldehyde-water shift ac talysis Aaron Rider Barnum Louisiana State University and Agricultural and Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Barnum, Aaron Rider, "Studies of a dirhodium tetraphosphine catalyst for hydroformylation and aldehyde-water shift catalysis" (2012). LSU Doctoral Dissertations. 3998. https://digitalcommons.lsu.edu/gradschool_dissertations/3998 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. STUDIES OF A DIRHODIUM TETRAPHOSPHINE CATALYST FOR HYDROFORMYLATION AND ALDEHYDE-WATER SHIFT CATALYSIS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College In partial fulfillment of the Requirements for the degree of Doctor of Philosophy In The Department of Chemistry by Aaron Rider Barnum B.S. Loyola University New Orleans, 2007 December 2012 ACKNOWLEDGEMENTS I would like to thank my family, for without their encouragements and support I would not be where I am today. To my parents, Otis and Cindy Barnum, thank you for everything throughout the years. To my grandmother Teruko, you are responsible for two things I hold very dear to my heart: inspiring me to become the scientist and chemist I am today and also for keeping me in touch with my Japanese heritage. -
CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R
CO2-Enabled Cyanohydrin Synthesis and Facile Homologation Reactions Martin Juhl†, Allan R. Petersen†, Ji-Woong Lee*,† †Department of Chemistry, Nano-Science Center, University of Copenhagen, Universitetsparken 5, Copenhagen Ø, 2100, Denmark KEYWORDS: Carbon Dioxide, Cyanohydrin, Xanthate, Homologation ABSTRACT: Thermodynamic and kinetic control of a chemical process is the key to access desired products and states. Changes are made when desired product is not accessible; one may manipulate the reaction with additional reagents, catalysts and/or protect- ing groups. Here we report the use of carbon dioxide to direct reaction pathways in order to selectively afford desired products in high reaction rates while avoiding the formation of byproducts. The utility of CO2-mediated selective cyanohydrin synthesis was further showcased by broadening Kiliani-Fischer synthesis to offer an easy access to variety of polyols, cyanohydrins, linear al- kylnitriles, by simply starting from alkyl- and arylaldehydes, KCN and atmospheric pressure of CO2. 9 A chemical reaction is governed by kinetics and ther- investigated the role of CO2 in a cyanation reaction, where CO2 modynamics, and a simultaneous control of both parameters is can be used in catalytic amounts to facilitate the stereoselective a common practice in designing and optimizing chemical reac- transformation of activated electrophiles via 1,4-conjugate ad- tions. The manipulation of thermodynamic stability of reactants dition reactions. Cyanohydrin synthesis - 1,2-cyanide addition and products -
Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis
UvA-DARE (Digital Academic Repository) Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis Lankelma, M.; Vreeken, V.; Siegler, M.A.; van der Vlugt, J.I. DOI 10.3390/inorganics7030028 Publication date 2019 Document Version Final published version Published in Inorganics License CC BY Link to publication Citation for published version (APA): Lankelma, M., Vreeken, V., Siegler, M. A., & van der Vlugt, J. I. (2019). Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis. Inorganics, 7(3), [28]. https://doi.org/10.3390/inorganics7030028 General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl) Download date:02 Oct 2021 inorganics Article Dinuclear Gold Complexes Supported by Wide Bite Angle Diphosphines for Preorganization-Induced Selective Dual-Gold Catalysis Marianne Lankelma 1, Vincent Vreeken 1, Maxime A. -
Uva-DARE (Digital Academic Repository)
UvA-DARE (Digital Academic Repository) Stereoge Phosphorus Containing Phosphine-Phosphite Ligands in Asymmetric Catalysis. Deerenberg, S. Publication date 2000 Link to publication Citation for published version (APA): Deerenberg, S. (2000). Stereoge Phosphorus Containing Phosphine-Phosphite Ligands in Asymmetric Catalysis. General rights It is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulations If you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: https://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. UvA-DARE is a service provided by the library of the University of Amsterdam (https://dare.uva.nl) Download date:25 Sep 2021 Chapterr 5 Nickell Phosphine-Phosphite Complexes as Catalysts in the Hydrocyanationn of Styrene Sinkk Deerenberg, Alison C. Hewat, Dieter Vogt, Paul C. J. Kamer, Piett W. N. M. van Leeuwen Abstract t Thee asymmetric hydrocyanation of styrene, catalyzed by chiral nickel phosphine- phosphitee complexes, gives the branched product nitrile in up to 34 % enantiomeric excess. Intermediatess in the catalytic cycle have been detected by 3,P{IH} NMR, including Ni(Pi- P2)(cod)) (A) and Ni(Pi-P2)(styrene) (B) (P1-P2 = ligands 1-5; cod = 1,5-cyclooctadiene). -
Transition Metal Complexes of a Novel Tetradentate Phosphine and of a New Diphosphine Ether Mark R
Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1991 Transition metal complexes of a novel tetradentate phosphine and of a new diphosphine ether Mark R. Mason Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Inorganic Chemistry Commons Recommended Citation Mason, Mark R., "Transition metal complexes of a novel tetradentate phosphine and of a new diphosphine ether " (1991). Retrospective Theses and Dissertations. 9554. https://lib.dr.iastate.edu/rtd/9554 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfîlm master. UMI films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from ary type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleedthrough, substandard margins, and improper alignment can adversely afreet reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. -
Communication
COMMUNICATION DOI: 10.1002/adsc.201500313 Rhodium(I)-Catalyzed Intermolecular Hydroacylation of α- Keto Amides and Isatins with Non-Chelating Aldehydes Kevin G. M. Kou,a,b Lauren E. Longobardi,b and Vy M. Donga* a University of California, Irvine, Department of Chemistry, Natural Sciences I, Irvine, California 92697, United States Fax: (949) 824-8571 Email: [email protected] b University of Toronto, Department of Chemistry, 80 St. George St., Toronto, ON, Canada M5S 3H6 Received: April 9, 2015 Dedicated to Prof. Stephen L. Buchwald on the occasion of his 60th birthday. Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######. Abstract. The application of the bidentate, electron-rich we sought to develop an analogous catalyst to enable bisphosphine ligand, 1,3-bis(dicyclohexyl)phosphine- a more general intermolecular transformation. To propane (dcpp), in rhodium(I)-catalyzed intermolecular study this challenging reaction, α-keto amide 2a was ketone hydroacylation is herein described. Isatins and α- chosen as the model ketone substrate, given its ability keto amides are shown to undergo hydroacylation with a to chelate metal centers.[15,16] In the presence of a variety of non-chelating linear and branched aliphatic bisphosphine ligand, chelation of the 1,2-keto amide aldehydes. Also reported is the synthesis of new bidentate unit with concomitant oxidative addition of a simple chiral phosphine ligands, and their application in aldehyde would prevent decarbonylation while hydroacylation is discussed. directing insertion of the ketone into the Rh(III)- hydride (Figure 1). Keywords: ketone; hydroacylation; rhodium; asymmetric catalysis; P ligands While progress has been made in selective C−H oxidation via transition-metal catalyzed ketone hydroacylation,[1-4] the field is still young compared to that of the related ketone hydrosilylation,[5] olefin [6] [7] hydrogenation, hydroformylation, and hydroacylation[8] transformations. -
Chemfile Vol.6 No 8
2006 VOLUME 6 NUMBER 8 Privileged Ligands DUPHOS AND BPE PHOSPHOLANE LIGANDS DSM MONOPHOS™ FAMILY CHIRALQUEST PHOSPHINE LIGANDS SOLVIAS® FERROLceNYL-BASed LIGANDS (S)-MonoPhosTM: a powerful ligand for asymmetric synthesis. sigma-aldrich.com Introduction Chemists are continually searching for novel, efficient chiral transition metal catalysts to effect ever more difficult transformations. Highly effective asymmetric catalytic systems Vol. 6 No. 8 offer the possibility of synthesizing either desired enantiomer pure from simple achiral Aldrich Chemical Co., Inc. starting materials, with the chiral products then being directly employed in natural 1 Sigma-Aldrich Corporation product synthesis. Research groups have spent much well-earned effort in designing 6000 N. Teutonia Ave. high performance ligand platforms2 that exhibit the following general characteristics: Milwaukee, WI 53209, USA 1) the synthesis should be economically viable and allow for systematic variations in the architecture; 2) most (if not all) members of the ligand family should be readily produced from milligram to kilogram scale; and 3) the ligands should bind strongly to the metal center as well as generate a highly active and selective catalyst system. To Place Orders Chiral salens,3 bisoxazolines,4 tartrate ligands,5 and cinchona alkaloids6 represent the Telephone 800-325-3010 (USA) original “privileged ligands” classes that effect a wide variety of transformations under FAX 800-325-5052 (USA) exceptional enantiocontrol and with high productivity. Impressively, R&D groups -
Dual Electrocatalysis Enables Enantioselective Hydrocyanation of Conjugated Alkenes Lu Song1, Niankai Fu1, Brian G
Dual Electrocatalysis Enables Enantioselective Hydrocyanation of Conjugated Alkenes Lu Song1, Niankai Fu1, Brian G. Ernst1, Wai Hang Lee1, Michael O. Frederick2, Robert A. DiStasio Jr.1*, Song Lin1* 1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853, USA 2Small Molecule Design and Development, Eli Lilly and Company, Indianapolis, IN 46285, USA *Correspondence to: [email protected], [email protected] Abstract: Chiral nitriles and their derivatives are prevalent in pharmaceuticals and bioactive compounds. Enantioselective alkene hydrocyanation represents a convenient and efficient approach for synthesizing these molecules. However, a generally applicable method featuring a broad substrate scope and high functional group tolerance remains elusive. Here, We address this long-standing synthetic problem using an electrocatalytic strategy. Electrochemistry allows for the seamless combination of tWo classic radical reactions—cobalt-mediated hydrogen-atom transfer and copper-promoted radical cyanation—to accomplish highly enantioselective hydrocyanation Without the need for stoichiometric oxidant. We harness electrochemistry’s unique feature of precise potential control to optimize the chemoselectivity of challenging substrates. Computational analysis sheds light on the origin of enantioinduction, for Which the chiral catalyst imparts a combination of attractive and repulsive non-covalent interactions that direct the enantio- determining C–CN bond formation. This discovery demonstrates the power of electrochemistry -
Development of P-Chirogenic Phosphine Ligands Based on Chemistry of Phosphine–Boranes: Searching for Novelty and Utility in Synthetic Organic Chemistry
No.174 No.174 ResearchResearch ArticleArticle Development of P-Chirogenic Phosphine Ligands Based on Chemistry of Phosphine–Boranes: Searching for Novelty and Utility in Synthetic Organic Chemistry Tsuneo Imamoto Chiba University Yayoi-cho, Inage-ku, Chiba 263-8522, Japan E-Mail: [email protected] This paper is dedicated to Professor Teruaki Mukaiyama on the occasion of his 90th birthday. Abstract: This paper describes the synthesis and utilization of P-chirogenic phosphine ligands, mainly by reviewing our study on this research area. Various optically pure P-chirogenic phosphine ligands have been synthesized by the use of phosphine–boranes as the intermediates more conveniently than the previously existing methods using phosphine oxides. Conformationally rigid P-chirogenic phosphine ligands bearing a bulky alkyl group such as the tert-butyl group and a small group like the methyl group at the phosphorus atoms exhibit excellent enantioselectivity and catalytic efficiency in transition-metal-catalyzed asymmetric reactions. 2,3-Bis(tert-butylmethylphosphino)quinoxaline (QuinoxP*) has been widely used as an efficient ligand in both academia and industry by virtue of its air-stability and high enantioinduction ability. Electron-rich P-chirogenic bisphosphine ligands have been used for the elucidation of the mechanism of rhodium-catalyzed asymmetric hydrogenations of enamides and related substrates, and it has been revealed that the hydrogenations proceed via Rh-dihydride intermediates and the enantioselection is determined at the step of formation of hexacoordinated Rh(III) complexes involving the bisphosphine ligand, dihydride, and the substrate. Keywords: P-Chirogenic phosphine ligands, Phosphine–borane, Design of chiral ligands, Catalytic asymmetric synthesis, Asymmetric hydrogenation, Enantioselection mechanism 1.