Design and Synthesis of Chiral Ligands and Their Applications in Transition

Total Page:16

File Type:pdf, Size:1020Kb

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. A new chiral tridentate NNN-type indan-Ambox ligand was designed and synthesized targeting the direct hydrogenation of unfunctionalized aryl and alkyl ketones. Successful examples of unfunctionalized ketone reduction in a enantioselective catalytic pathway display the potential of tridentate ligands in asymmetric catalysis. Another rational design and synthesis of PNP-type bulky chiral tridentate ligand was also fulfilled, yet it failed to provide superior enantioselectivity. To solve the problems of asymmetric hydrogenation of imines and heteroaromatics, a series of Ir- or Pd-based catalyst systems have been developed. Highly enantioselective and highly efficient hydrogenation of N- iv aryl imine, N-H imines, β-enamine esters, quinoline derivatives and unprotected indole derivatives have been successfully achieved respectively, with up to 98% ee and 10,000 TON. Catalyst systems containing strongly electron-donating and sterically hindered bisphosphine ligand have displayed significant advantages and will lead to more updated breakthroughs. Other examples of transition metal-catalyzed reactions such as Cu- catalyzed conjugate reduction of cyclic α,β-unsaturated ketones and Ru-catalyzed dynamic kinetic resolution of α-substituted cyclic ketones have also been investigated. Some preliminary results were discussed accordingly. v TABLE OF CONTENTS LIST OF FIGURES ..................................................................................................... vii LIST OF SCHEMES.................................................................................................... ix LIST OF TABLES ....................................................................................................... xi ACKNOWLEDGEMENTS ......................................................................................... xiii Chapter 1 Introduction and Background .................................................................... 1 1.1 Introduction ..................................................................................................... 1 1.2 Chiral Ligands for Asymmetric Hydrogenation ............................................. 2 1.3 Conclusion ...................................................................................................... 13 References and Notes ........................................................................................... 16 Chapter 2 Synthesis of C3*-TunePhos Chiral Diphosphine Ligands and Their Applications in Asymmetric Hydrogenation of Unfunctionalized Ketones and Ketoesters ............................................................................................................. 24 2.1 Introduction and Background ......................................................................... 24 2.1.1 Synthesis of BINAP and Its Derivatives .............................................. 25 2.1.2 Synthesis of Atropisomeric Biaryl Ligands ......................................... 27 2.1.3 General Strategies of Synthesizing of Atropisomeric Biaryl Ligands ................................................................................................... 29 2.2 Results and Discussion ................................................................................... 30 2.2.1 TunePhos and C3*-TunePhos Ligand Synthesis .................................. 30 2.2.2 Alternative Efficient Synthesis of C3*-TunePhos and Related Bisaminophosphine Ligands .................................................................. 37 2.2.3 Ru-C3*-TunePhos Catalyzed Asymmetric Hydrogenations ................ 39 2.2.4 Rh-Bisaminophosphine Catalyzed Asymmetric Hydrogenations ........ 47 2.3 Conclusion ...................................................................................................... 50 Experimental Section ............................................................................................ 51 References and Notes ........................................................................................... 68 Chapter 3 Synthesis of Chiral Tridentate Ligands and Their Application in Enantioselective Hydrogenation Unfunctionalized Ketones ................................ 74 3.1 Introduction and Background ......................................................................... 74 3.2 Results and Discussion ................................................................................... 77 3.2.1 Development of Indan-Ambox Ligand and Its Application in the Hydrogenation of Unfunctionalized Ketone .......................................... 77 vi 3.2.2 Synthesis of PNP-Type Ligand and Its Application in the Hydrogenation of Unfunctionalized Ketone .......................................... 86 3.3 Conclusion ...................................................................................................... 90 Experimental Section ............................................................................................ 90 References and Notes ........................................................................................... 104 Chapter 4 Ir-Catalyzed Asymmetric Hydrogenation of Imines, Enamine Esters and Heteroaromatics ............................................................................................. 109 4.1 Introduction and Background ......................................................................... 109 4.2 Results and Discussion ................................................................................... 111 4.2.1 Ir-Catalyzed Asymmetric Hydrogenation of N-Aryl Imines ................ 111 4.2.2 Ir-Catalyzed Asymmetric Hydrogenation of N-H Imines .................... 121 4.2.3 Ir-Catalyzed Asymmetric Hydrogenation of Unprotected β- Enamine Esters ....................................................................................... 129 4.2.4 Ir-Catalyzed Asymmetric Hydrogenation of Quinoline Derivatives .... 136 4.2.5 Pd-Catalyzed Asymmetric Hydrogenation of 2-Indole Derivatives .... 141 4.3 Conclusion ...................................................................................................... 144 Experimental Section ............................................................................................ 145 References and Notes ........................................................................................... 180 Chapter 5 Metal-Catalyzed Asymmetric Conjugate Reduction and Dynamic Kinetic Resolution ................................................................................................ 192 5.1 Introduction and Background ......................................................................... 192 5.1.1 Cu-Catalyzed Asymmetric Conjugate Reduction ................................ 192 5.1.2 Ru-Catalyzed Dynamic Kinetic Resolution ......................................... 195 5.2 Results and Discussion ................................................................................... 196 5.2.1 Cu-Catalyzed Asymmetric Conjugate Reduction ................................ 196 5.2.2 Structural Modification and Modified Ligand Synthesis ..................... 202 5.2.3 Ru-Catalyzed Dynamic Kinetic Resolution ......................................... 205 5.3 Conclusion ...................................................................................................... 208 Experimental Section ............................................................................................ 209 References and Notes ........................................................................................... 217 vii LIST OF FIGURES Figure 1-1: Early Development in Chiral Phosphorus Ligands. .................................
Recommended publications
  • Modern-Reduction-Methods.Pdf
    Modern Reduction Methods Edited by Pher G. Andersson and Ian J. Munslow Related Titles Yamamoto, H., Ishihara, K. (eds.) Torii, S. Acid Catalysis in Modern Electroorganic Reduction Organic Synthesis Synthesis 2008 2006 ISBN: 978-3-527-31724-0 ISBN: 978-3-527-31539-0 Roberts, S. M. de Meijere, A., Diederich, F. (eds.) Catalysts for Fine Chemical Metal-Catalyzed Cross- Synthesis V 5 – Regio and Coupling Reactions Stereo-Controlled Oxidations 2004 and Reductions ISBN: 978-3-527-30518-6 2007 Online Book Wiley Interscience Bäckvall, J.-E. (ed.) ISBN: 978-0-470-09024-4 Modern Oxidation Methods 2004 de Vries, J. G., Elsevier, C. J. (eds.) ISBN: 978-3-527-30642-8 The Handbook of Homogeneous Hydrogenation 2007 ISBN: 978-3-527-31161-3 Modern Reduction Methods Edited by Pher G. Andersson and Ian J. Munslow The Editors All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and Prof. Dr. Pher G. Andersson publisher do not warrant the information Uppsala University contained in these books, including this book, to Department of Organic Chemistry be free of errors. Readers are advised to keep in Husargatan 3 mind that statements, data, illustrations, 751 23 Uppsala procedural details or other items may Sweden inadvertently be inaccurate. Dr. Ian J. Munslow Library of Congress Card No.: Uppsala University applied for Department of Biochemistry and Organic Chemistry Husargatan 3 British Library Cataloguing-in-Publication Data 751 23 Uppsala A catalogue record for this book is available from Sweden the British Library. Bibliographic information published by the Deutsche Nationalbibliothek Die Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografi e; detailed bibliographic data are available on the Internet at <http://dnb.d-nb.de>.
    [Show full text]
  • MICROREVIEW Substrate Activation in the Catalytic Asymmetric
    MICROREVIEW B. Balakrishna, J. L. Núñez-Rico, A. Vidal-Ferran This is the peer reviewed version of the following article: Eur. J. Org. Chem. 2015, 5293–5303, which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201500588/pdf. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving." Substrate Activation in the Catalytic Asymmetric Hydrogenation of N-Heteroarenes Bugga Balakrishna,[a] José Luis Núñez-Rico[a] and Anton Vidal-Ferran*[a],[b] Keywords: Asymmetric catalysis / Enantioselectivity / Iridium / Palladium / Nitrogen heterocycles / Hydrogenation. Different methods for transforming N-heteroarenes into more reactive derivatives for catalytic asymmetric hydrogenation are highlighted. The first strategy consists of facilitating hydrogenation by the formation of positively charged derivatives of the heteroarene. Catalyst deactivation processes arising upon binding of the substrate to the metal center can thus be prevented and, additionally, hydrogenation of positively charged heteroarenes may also be more favored than that of their neutral analogues. The second strategy is based on introducing a ligating group onto the substrate to assist its coordination to the metal center and facilitate hydrogenation by chelation assistance. The last strategy involves breaking the aromaticity of the heteroarene by inducing a doublebond migration process. This microreview summarizes advances made in the above strategies, which have allowed the development of highly enantioselective catalytic hydrogenation of N-heteroarenes for the production of fully or partially saturated chiral heterocycles. Introduction synthesizing fully or partly reduced heteroaromatic derivatives in Enantiopure organic compounds are important constituents of enantiomerically pure form (Scheme 1).[8] This synthetic strategy commercially produced chemicals including plastics, active also benefits from a great diversity of starting materials.
    [Show full text]
  • Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols
    Iridium Catalysed Asymmetric Hydrogenation of Olefins and Isomerisation of Allylic Alcohols Byron Peters ©Byron Kennedy Peters, Stockholm University 2015 ISBN 978-91-76492-79-6 Printed in Sweden by Holmbergs, Malmö 2015 Distributor: Department of Organic Chemistry, Stockholm University ii Abstract The work described in this thesis is focused on exploring the efficacy of asymmetric iridium catalysis in the hydrogenation of challenging substrates, including precursors to chiral sulfones and chiral cyclohexanes. Further- more, iridium catalysis was used to isomerise allylic alcohols to aldehydes, and in a formal total synthesis of Aliskiren (a renin inhibitor). A large varie- ty of unsaturated sulfones (cyclic, acyclic, vinylic, allylic and homoallylic) were prepared and screened in the iridium catalysed hydrogenation reaction using a series of previously developed N,P-ligated Ir-catalysts. The outcome was a highly enantioselective (>90% ee) protocol to prepare sulfones bearing chiral carbon scaffolds, sometimes having purely aliphatic substituents at the stereogenic centre. Furthermore, performing the Ramberg-Bäcklund reaction on the chiral products, under optimised conditions, produced cyclic and acy- clic unsaturated derivatives without erosion of enantiomeric excess. This hydrogenation protocol was also successful in the hydrogenation of a num- ber of cyclohexene-containing compounds. Minimally functionalised, func- tionalised and heterocycle-containing cyclohexenes were hydrogenated in up to 99% ee. Hitherto, both chiral sulfones and chiral cyclohexanes have been challenging targets for most catalytic asymmetric methodologies. Although the preparation of aldehydes and ketones by isomerisation of the correspond- ing allylic alcohol is well established, there has been limited success in the development of good enantioselective protocols. For the isomerisation of a number -allylic alcohols to the corresponding chiral aldehydes, high enan- tioselectivities (up to >99% ee) and modest yields were achieved using an N,P-iridium catalyst.
    [Show full text]
  • 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.
    [Show full text]
  • The Noyori Asymmetric Hydrogenation Reaction Chem 115
    Myers The Noyori Asymmetric Hydrogenation Reaction Chem 115 Reviews: Mechanism: 1/n {[(R)-BINAP]RuCl2}n Noyori, R. Angew. Chem. Int. Ed. 2013, 52, 79–92. • Catalytic cycle: 2 CH3OH Kitamura, M.; Nakatsuka, H. Chem. Commun. 2011, 47, 842–846. Tang, W.; Zhang, X. Chem. Rev. 2003, 103, 3029–3069. Noyori, R.; Ohkuma, T. Angew. Chem. Int. Ed. 2001, 40, 40–73. [(R)-BINAP]RuCl2(CH3OH)2 H2 OCH3 Original Report by the Noyori Group: O HCl CH3OH O [(R)-BINAP]RuHCl(CH3OH)2 CH3 H2 2 CH OH H2 (100 atm) 3 O O OH O RuCl2[(R)-BINAP] (0.05 mol %) OCH3 CH3 OCH3 CH3 OCH3 CH3OH, 36 h, 100 °C O [(R)-BINAP]RuCl(CH3O)(CH3OH)2 [(R)-BINAP]HClRu 96%, >99% ee O OCH 3 CH3 O OCH3 HO O Noyori, R., Okhuma, T.; Kitamura, M.; Takaya, H.; Sayo, N.; Kumobayashi, H.; Akuragawa, S. CH OH CH3 3 J. Am. Chem. Soc. 1987, 109, 5856–5858. [(R)-BINAP](CH3OH)ClRu 2 CH3OH O CH3 • Both enantiomers of BINAP are commercially available. Alternatively, both enantiomers can be Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley & Sons: New York, 1993, prepared from the relatively inexpensive (±)-1,1'-bi-2-naphthol. pp. 56–82. • The reduction of methyl 2,2-dimethyl-3-oxobutanoate proceeds in high yield and with high enantioselectivity, providing evidence that the reduction proceeds through the keto form of the !-keto ester. However, pathways that involve hydrogenation of the enol form of other !-keto esters cannot be OH PPh2 PPh2 ruled out. + OH PPh2 PPh2 H2 (100 atm) O O OH O RuCl2[(R)-BINAP]–Ru (±)-1,1'-Bi-2-naphthol (R)-(+)-BINAP (S)-(–)-BINAP CH3 OCH3 CH OH, 23 °C CH3 OCH3 20% 20% 3 CH3 CH3 CH3 CH3 99%, 96% ee Takaya, H.; Akutagawa, S.; Noyori, R.
    [Show full text]
  • Interrupted Pyridine Hydrogenation: Asymmetric Synthesis of Δ‐Lactams
    Angewandte Communications Chemie How to cite: Asymmetric Catalysis Hot Paper International Edition: doi.org/10.1002/anie.202016771 German Edition: doi.org/10.1002/ange.202016771 Interrupted Pyridine Hydrogenation: Asymmetric Synthesis of d-Lactams Tobias Wagener+, Lukas Lckemeier+, Constantin G. Daniliuc, and Frank Glorius* Dedicated to Professor David A. Evans on the occasion of his 80th birthday Abstract: Metal-catalyzed hydrogenation is an effective method to transform readily available arenes into saturated motifs, however, current hydrogenation strategies are limited to the formation of CÀH and NÀH bonds. The stepwise addition of hydrogen yields reactive unsaturated intermediates that are rapidly reduced. In contrast, the interruption of complete hydrogenation by further functionalization of unsaturated intermediates offers great potential for increasing chemical complexity in a single reaction step. Overcoming the tenet of full reduction in arene hydrogenation has been seldom demonstrated. In this work we report the synthesis of sought- after, enantioenriched d-lactams from oxazolidinone-substi- tuted pyridines and water by an interrupted hydrogenation mechanism. Metal-catalyzed hydrogenation is known to be a simple and powerful method to increase molecular complexity.[1] In particular, the hydrogenation of easily accessible N-hetero- arenes such as pyridines offers access to important saturated azacycles.[2] This established reaction is limited solely to the formation of new CÀH and NÀH bonds; additional synthetic Figure 1. Mechanistic pathways of unsaturated intermediates in arene manipulations are required to introduce further chemical hydrogenation and this work. Aux =chiral auxiliary. functionality.[3] The stepwise transfer of molecular hydrogen in arene hydrogenation yields intermediates with double synthesized using iridium-catalyzed hydride transfer followed bonds remaining, which in principle offer the possibility of by hydroxymethylation.
    [Show full text]
  • Application of Hydrogen Bonding in Asymmetric
    APPLICATION OF HYDROGEN BONDING IN ASYMMETRIC HYDROGENATION By JIALIN WEN A dissertation submitted to the Graduate School-New Brunswick Rutgers, The State University of New Jersey In partial fulfillment of the requirements For the degree of Doctor of Philosophy Graduate Program in Chemistry and Chemical Biology Written under the direction of Professor Xumu Zhang And approved by _____________________________________ _____________________________________ _____________________________________ _____________________________________ New Brunswick, New Jersey October, 2016 ABSTRACT OF THE DISSERTATION Application of Hydrogen Bonding in Asymmetric Hydrogenation By JIALIN WEN Dissertation Director: Xumu Zhang Hydrogen bonding has been widely observed in biosynthesis and enzyme catalysis. It plays an important role in such fields as molecular recognition, supramolecular chemistry and small molecule catalysis. A new concept of organocatalysis emerged in recent two decades. Hydrogen bonding is the keystone for thiourea catalysis or phosphoric acid catalysis. With high turnover numbers and excellent enantioselectivity, transition metal catalysis not only is the arts in academia, but also find its merit in industrial application. Homogeneous hydrogenation, among many successful transition metal catalyzed reactions, has been serving the synthetic communities for many years, both in academia or in industry. The success of secondary interaction and hydrogen bonding offer us an alternative: the combination of hydrogen bonding and steric hindrance help to create a chiral environment in which substrates could be reduced efficiently. ii Guided by this rationale, a ferrocene-based bisphosphine/thiourea ligand, ZhaoPhos was synthesized in our group. It was applied in the asymmetric hydrogenation of nitroolefins with hydrogen bonding between the ligand and substrates. Thiourea- carbonyl hydrogen bonding is another model of non-covalent interaction.
    [Show full text]
  • Synthesis of Iron Carbonyl Complexes 64
    FAKULTÄT FÜR CHEMIE Lehrstuhl für Strukturanalytik in der Katalyse The Synthesis, Characterization and Performance of Well-Defined Iron Carbonyl Catalysts Hüseyin Güler Vollständiger Abdruck der von der Fakultät für Chemie der Technischen Universität München zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften genehmigten Dissertation. Vorsitzender : Univ.-Prof. Dr. Klaus Köhler Prüfer der Dissertation: 1. Prof. Moniek Tromp, Ph.D. Univ. Amsterdam / Niederlande 2. Univ.-Prof. Dr. Thomas Brück Die Dissertation wurde am 28.05.2015 bei der Technischen Universität München eingereicht und durch die Fakultät für Chemie am 28.07.2015 angenommen. i THE SYNTHESIS, CHARACTERIZATION AND PERFORMANCE OF WELL-DEFINED IRON CARBONYL CATALYSTS HUSEYIN GULER Doctoral Thesis Technische Universität München May 2015 ii Hüseyin Güler: The Synthesis, Characterization and Performance of Well-Defined Iron Carbonyl Catalysts. © May 2015 iii ABSTRACT The synthesis of well-defined, uniform iron carbonyl based complexes incorporating disphoshine ligands was performed and their performance as homogeneous catalysts evaluated. The iron carbonyl diphosphine complexes were formed by reaction of Fe3(CO)12 and bidentate diphosphine ligands. Detailed characterizations as well as kinetic studies were performed to provide fundamental insights in the catalyst properties. These iron carbonyl complexes were examined as homogeneous catalysts in 2-propanol-based transfer hydrogenation of ketone. The influence of different reaction parameters on the catalytic performance was investigated. The scope and limitations of the described catalyst for the reduction of a series different ketones was shown. In most cases, high conversion and selectivity are obtained. Mechanistic and kinetic studies indicate a monohydride reaction pathway for the homogeneous iron catalyst. Iron carbonyls supported on γ-Al2O3 were obtained and their performance as heterogeneous catalysts evaluated.
    [Show full text]
  • 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
    [Show full text]
  • Asymmetric Hydrogenation As Ideal Green Chemistry
    AsymmetrProc Indianic Natn Hydrog Sci Acadenation 72 asNo.4 Ideal pp. 267-273Green Chemistry (2006) 267 Review Article Asymmetric Hydrogenation as Ideal Green Chemistry RYOJI NOYORI RIKEN, Wako, Saitama 351-0198, Japan, and Department of Chemistry and Research Center of Materials Science, Nagoya University, Chikusa, Nagoya 464-8062, Japan (Received 4 November 2006; Accepted 16 December 2006) We should be proud of being chemists. Chemistry is more important compounds in a cost-effective, energy-saving, than a science of observing and understanding Nature. and environmentally benign manner. The world maket It is characterized by the capability of generating high of catalysts is ca. 12B USD, and the chemical production values from almost nothing. Therefore, synthesis is not through catalysis is estimated to be 1.2-6.0T USD. merely an intellectual challenge but also a practical Therefore, chemists must develop practical catalytic technology for the survival of our species. Man-made processes using heterogeneous, homogeneous, and substances and materials determine the quality of life. biological catalysts. In fact, throughout the history of humankind, chemistry Since long before the significance of Green has been essential to the prosperity of society [1]. Its Chemistry became apparent, I have pursued significance is ever increasing. hydrogenation, the ultimate Green Technology. In 2003, the National Academy of Engineering in Hydrogen is a clean and abundant resource and has the US characterized the 20th century as “A Century of unlimited applicability to basic and applied science, Innovation” and selected 20 greatest technologies that technology, and industry at large. In particular, decisively changed our lives during that period [2].
    [Show full text]
  • Ligand 960 Accessible Molecular Surfa
    1699 Index a acrylate 199, 1612 abiraterone 426 – derivatives 1115, 1117 abnormal lactone (AL) 1495, 1496 – esters, synthesis of 1610 π-acceptors 828 acrylic acid 126, 1612 – π*-acceptor 810 – based on CO2 1610 – ligand 960 – thermodynamic situation 1611 accessible molecular surface (AMS) 834 acrylonitrile-butadiene-polystyrene acenaphthene imine derivative ligands 257 microencapsulated Os 1514 acetaldehyde 508 actinides 1071 – from ethylene 500 activated carbon 1343 – oxidation 95 activation energy 963 acetamide, transamidation of activation reaction 233 – amino acid catalyzed 1436 active catalyst system 283 acetic acid 93, 709, 1526 active noble metal complexes, reoxidation – nickel-based catalysts 105 1264 acetic anhydride 110, 111 acyclic diene metathesis polymerization 2´-acetonaphthone 735 (ADMET) 824 acetonitrile 708, 1547 acyclic ketones, BV oxidation of 1502 acetophenones 726, 730, 732, 734, 738, 1047 acyclic precursors 1343 – derivatives 726 N-acyl-α-amino acid derivatives acetylcholinesterase (AChE) inhibitor 1496 – synthesis 1197 acetylide ligand acylamidines 1469 – on photocatalytic H2 production 1668 N-acyl amino acids 1535 N-acetylmannosamine (ManNAc) 920 acylases 913 (+)-achalensolide, asymmetric synthesis 1300 N-acyl cyclic amines 1535 acid–amine coupling 1429 acyl hydrazones, with Rh/duphos 633 – boron derivative 1429 acyl ligand 103 acid–base interactions 860 acyl palladium complex 169 acid halides 525 acylphosphite 838 acidic hydrogen ion 492 1-adamantanol 1533 π-acidic ligands 1404 adapalene 429 acidic phosphate electrolyte, electrochemical adenine-thymine (A-T) 858 properties 1142 adiabatic flash 100 acids, promotor effect 1268 adipic acid Acinetobacter calcoaceticus 908 – fermentation of 1617 – NCIMB 9871 909 – production from LA 1629 acridine-based bisphosphine ligand 1629 aerobic oxidation 1057 acrolein acetal, Heck arylation of 974 Ag/Al2O3 catalyst 1445 acrolein, arylation 974 alcohol dehydrogenase (ADH) 901, 903 Applied Homogeneous Catalysis with Organometallic Compounds: A Comprehensive Handbook in Four Volumes, Third Edition.
    [Show full text]
  • TRANSITION-METAL-CATALYZED HYDROACYLATION Vy M. Dong, Kevin G. M. Kou, and Diane N. Le Department of Chemistry, University of Ca
    TRANSITION-METAL-CATALYZED HYDROACYLATION Vy M. Dong, Kevin G. M. Kou, and Diane N. Le Department of Chemistry, University of California, Irvine, California 92697-2025, United States Vy M. Dong: [email protected] ACKNOWLEDGEMENTS Our work in this area has been supported by UC Irvine, the National Institutes of Health (GM105938), and NSERC. We also acknowledge Paul Feldman for his editorial assistance in compiling the chapter as well as Scott Denmark for the opportunity to contribute to Organic Reactions. INTRODUCTION Transition-metal catalysis has revolutionized the way natural products and medicinal targets are made. For example, asymmetric hydrogenation, olefin metathesis, and cross-coupling have evolved into indispensable tools for drug discovery. As a complement to these well-established strategies, the metal-catalyzed activation of C─H bonds is an increasingly valuable and attractive approach. In metal-catalyzed hydroacylation, an aldehyde C─H bond is oxidized to generate either a C─C bond or C─O bond, depending on the coupling partner used (e.g., alkene, alkyne, or carbonyl compound). This strategy represents an attractive, atom-economical approach for building both ketones and esters from aldehydes (Scheme 1). (1) To date, hydroacylation is most well-established for the preparation of five-membered rings, typically by rhodium catalysis. As the tether between the aldehyde and the unsaturated coupling partner becomes longer, decarbonylation becomes favored over hydroacylation. Similarly, the rate of decarbonylation is usually greater than the rate of hydroacylation in intermolecular reactions. The desired transformation is more favorable, however, when coodinating or directing groups are present on the substrate (Schemes 2 and 3).
    [Show full text]