DOCSLIB.ORG

Recent Advances of BINAP Chemistry in the Industrial Aspects

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Recent Advances of BINAP Chemistry in the Industrial Aspects NEW TOOLS IN SYNTHESIS 1055 Recent Advances of BINAP Chemistry in the Industrial Aspects Hidenori Kumobayashi, Takashi Miura,* Noboru Sayo, Takao Saito, Xiaoyong Zhang Central Research Laboratory, Takasago International Corporation, 1-4-11 Nishi-yawata, Hiratsuka, Kanagawa 254-0073, Japan Fax (0463)25-2084; E-mail: [email protected] Received 24 April 2001 and ketones such as a-(acylamino)acrylic acids,6 enam- Abstract: New efficient synthetic methods of optically active BI- 7 8 ides, a,b-unsaturated carboxylic acids, allylic and ho- NAP [BINAP = 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl] and 9 10 its variants are described. Application of these BINAP variants in moallylic alcohols, alkylidene lactones, alkenyl 10 11 12 asymmetric catalytic hydrogenation of prochiral ketones and olefins ethers, b-keto esters, b-hydroxyketones, and b-ami- to various industrially important compounds is discussed. noketones.12 Key words: BINAP ligands, ruthenium and iridium catalysts, Starting with the development of l-menthol process using asymmetric hydrogenation, ketones, unsaturated carboxylic acids BINAP–Rh catalyzed asymmetric isomerization of allyl- amines,5a we have been investigating catalytic asymmet- ric synthesis mainly based on BINAP chemistry for two Introduction decades and have developed various asymmetric synthet- ic processes. All of these results are based on the success Enantioselective syntheses have been gaining more and of the marvelous abilities of the BINAP ligands. Recently more importance in a wide range of fields such as pharma- the targets of asymmetric synthesis have become varied ceuticals, agrochemicals, food additives, aromachemicals and complicated, while BINAP sometimes shows its lim- and functional materials because the biological activities itation. It becomes necessary to develop new ligands to of these materials are often associated with their absolute compensate for the limitations of BINAP. In this paper we configuration. described recent developments of BINAP chemistry, es- pecially about syntheses and applications of new BINAP Known methods to obtain enantiomerically pure com- ligands from the industrial point of view. pounds are classified as follows: 1) optical resolution, 2) modification of naturally occurring materials, 3) biologi- cal transformation, and 4) asymmetric catalysis using a New Synthetic Methods of BINAP and Its Variants prochiral compound as the starting material. Among these methods, asymmetric catalysis is emerging as one of the Since the practical methods for synthesis of 2,2’-bis(dia- most efficient and versatile methods for the preparation of rylphosphino)-1,1’-binaphthyls (BINAPs) were reported a wide range of chiral target molecules. In recent years, in 1986,13 a series of BINAP analogues have been pre- numerous catalytic asymmetric reaction processes that pared. However, this route requires harsh conditions for transform prochiral substrates into chiral products with 1 the conversion of binaphthol to the corresponding dibro- high enantioselectivity have been developed. Asymmet- mide and tedious optical resolution of BINAP derivatives ric hydrogenation is one of the most powerful tools for the (Scheme 1). synthesis of enantiomerically pure compounds. For this purpose, several kinds of metal–optically active phos- Recently, Cai et al. of Merck developed a new method for phine complexes have been synthesized so far. In general, direct asymmetric synthesis of BINAP by use of nickel- catalyzed coupling reaction of easily accessible chiral a chiral transition metal catalyst precursor LnM can be re- garded as composed of two key parts, the chiral ligand L 2,2’-bis((trifluoromethanesulfonyl)oxy)-1,1’-binaphthyl and the central metal M. Thus, the proper combination of (1) with diphenylphosphine in the presence of DABCO 14 well-designed chiral ligands and selected metals is the (Scheme 2). Similarly, Laneman et al. of Monsanto re- most important requirement for high catalytic efficiency. ported the nickel-catalyzed cross-coupling of 1 with chlo- 15 Over the past twenty-five years, various kinds of chiral rodiphenylphosphine in the presence of zinc. These phosphines have been developed by researchers in methods, however, have some drawbacks in industrializa- academic, pharmaceutical and fine chemical companies. tion, such as use of pyrophoric diphenylphosphine or Among them, 2,2’-bis(diphenylphosphino)-1,1’- moisture-sensitive chlorodiphenylphosphine. binaphthyl2 (BINAP) has been found to have remarkable On the other hand, we have explored two unique proce- chiral recognition ability and broad applicability in vari- dures for the synthesis of chiral BINAPs by using the met- ous transition metal-catalyzed asymmetric reactions such al-catalyzed coupling reaction of 1 with diarylphosphine as hydrogenation,3 hydrosilylation,4 1,3-hydrogen migra- oxides, which are readily prepared by the reaction of aryl- tion,5 etc. For example, BINAP–ruthenium catalysts are magnesium halide with diethyl phosphite and easy to han- well recognized to be highly efficient catalysts for asym- dle in large quantity.16 The first one is well illustrated by metric hydrogenations of various functionalized olefins coupling of (R)-1 with diphenylphosphine oxide, which Synlett 2001, No. SI, 1055–1064 ISSN 0936-5214 © Thieme Stuttgart · New Yorkrt · New York 1056 H. Kumobayashi et al. NEW TOOLS IN SYNTHESIS Biographical Sketches Hidenori Kumobayashi thol with enantioselective cal Society of Japan Award was born in Niigata, Japan. isomerization of allylamines for Technical Development. In 1967 he obtained a B.S. catalyzed by BINAP—Rh(I) He is now a vice president at degree from Shinsyu Univer- complexes as the key reac- Takasago International Cor- sity and joined Takasago In- tion. This was followed by poration and the general ternational Corporation. In studies on efficient synthesis manager of Fine Chemical 1986 he earned his Ph. D. of key intermediates of car- Devision. His main research from Osaka University under bapenem antibiotics by using interests include asymmetric the direction of Prof. Sei Ot- BINAP—Ru(II)-catalyzed synthesis using transition suka where he worked on de- asymmetric hydrogenation metal catalysts. velopment of industrial of ketone compounds. In synthetic process of l-men- 1997 he received the Chemi- Takashi Miura obtained a nonium salts with Prof. Paul Central Research Laboratory Ph.D. from Tokyo Metropol- G. Gassman at University of of Takasago International itan University in 1979 under Minnesota from 1979 to Corporation. Like his collab- the guidance of Prof. Michio 1981. In 1982 he joined orator, he is convinced that Kobayashi. He pursued post- Takasago International Cor- asymmetric catalysis offers doctoral research on the 2,3- poration and is now general many attractive options for sigmatropic rearrangement manager at Fine & Aroma organic chemist and indus- of sulfonium salts and sele- Chemical Laboratory in try. Noboru Sayo, born in join the Professor Nakai’s re- Central Research Laboratory Hyogo, Japan, in 1954, stud- search group and worked in of Takasago International ied applied chemistry at the field of carbanion chem- Corporation. His main re- Shinsyu University, and ob- istry. After obtaining his search interests have been tained his M. S. degree in ap- Ph.D. in 1984, he entered associated with the develop- plied chemistry from Takasago International Cor- ment of catalytic asymmetric Okayama University in poration. Now he is assistant synthesis. 1979. He moved to Tokyo director at Fine & Aroma Institute of Technology to Chemical Laboratory in Takao Saito was born in his Ph. D. from Osaka Uni- of Takasago International Ibaraki (Japan) in 1960. He versity under supervision of Corporation. His current obtained his M.S. degree Prof. Shun-ichi Murahashi in area of research includes the from Meiji College of Phar- 1996 and is now research as- development of new molecu- macy in 1985 and then sociate at Fine & Aroma lar catalysts. joined Takasago Internation- Chemical Laboratory in al Corporation. He received Central Research Laboratory Xiaoyong Zhang was born University under supervision tory in Central Research in Zhejiang, China and re- of the late Prof. Hidemasa Laboratory. He is pursuing ceived his M.S. degree in or- Takaya in 1994 and then exploration of new efficient ganic chemistry at Institute joined Takasago Internation- synthetic methods of chiral of Chemistry, Chinese Acad- al Corporation where he is ligands and their application emy of Sciences in 1987. He now a senior chemist at Fine to asymmetric catalysis. earned his Ph.D. from Kyoto & Aroma Chemical Labora- Synlett 2001, No. SI, 1055–1064 ISSN 0936-5214 © Thieme Stuttgart · New York NEW TOOLS IN SYNTHESIS Recent Advances of BINAP Chemistry in the Industrial Aspects 1057 OH i)Br ii)MgBr iii) OH Br MgBr rac-Binaphthol rac-Dibromide iv—vi) vii) P(O)Ph2 P(O)Ph2 PPh2 P(O)Ph2 P(O)Ph2 PPh2 rac-BINAPO (R)-(+)-BINAPO (R)-(+)-BINAP - Scheme 1 i) Br2, PPh3, 230 °C; ii) Mg; iii) Ph2P(O)Cl; iv) (2R,3R)-( )-di-O-benzoyltartaric acid; v) fractional crystallization; vi) NaOH; vii) Cl3SiH, PhNMe2. toluene, giving (R)-BINAP in 96% yield. This procedure has been successfully applied to the synthesis of a series of known or new chiral BINAP ligands in reasonable to OTf a or b PPh 2 good yields. It is noteworthy that most of these new BI- OTf PPh 2 NAPs had been difficult to obtain through the optical res- olution route shown in Scheme 1. However, when (R)-2,2’-bis((trifluoromethanesulfo- (R)- or (S)-1 (R)- or (S)-BINAP nyl)oxy)-5,5’,6,6’,7,7’,8,8’-octahydro-1,1’-binaphtyl
Load more

Recommended publications
  • The Synthesis of Molecules Containing Quaternary Stereogenic Centers Via the Intramolecular Asymmetric Heck Reaction
    The Synthesis of Molecules Containing Quaternary Stereogenic Centers via the Intramolecular Asymmetric Heck Reaction Reported by Eric P. Gillis April 19, 2007 INTRODUCTION The enantioselective synthesis of compounds containing quaternary stereocenters continues to be a challenging endeavor and is a field of intense interest and development.1,,,,2 3 4 5 From the perspective of methods development, the asymmetric synthesis of compounds containing quaternary stereocenters poses a distinct challenge due to the sterically congested environment in which C-C bonds must be formed and stereochemical information must be transferred. Existing asymmetric methods have been applied successfully in desymmetrization processes that transform prochiral quaternary centers into stereodefined quaternary centers. However, for processes in which a quaternary stereocenter is created directly via a C-C bond forming reaction, only a few asymmetric reactions have been fruitful. The diversity in the array of methods that exist for the synthesis of compounds containing quaternary stereocenters is necessitated in part because of the number of distinct quaternary stereocenter architectures that are possible (Scheme 1). The construction of acyclic quaternary stereocenters is particularly challenging due to the number of degrees of freedom associated with these structures. However, promising results for the construction of these stereocenters via allylation,6 allylic alklyation,7 and Michael addition8 have been reported recently. For the synthesis of cyclic quaternary stereocenters a number of methods have been employed successfully including the intramolecular Heck reaction,9 alkylation,10 arylation,11 and Michael addition12. Fused bicyclic quaternary stereocenters are generally accessed via the desymmetrization of a prochiral quaternary center. In this regard, theoretically any SCHEME 1.
    [Show full text]
  • Diphosphine Complexes on Alpo4-Sepiolite Supports
    catalysts Article Hydrogenation of α,β-Unsaturated Carbonyl Compounds over Covalently Heterogenized Ru(II) Diphosphine Complexes on AlPO4-Sepiolite Supports Verónica Caballero 1, Rafael Estevez 1, Diego Luna 1,* , Felipa M. Bautista 1 , Antonio A. Romero 1 , Laura Aguado-Deblas 1 , Jesús Hidalgo-Carrillo 1 and Isabel Romero 2 1 Departamento de Química Orgánica, Campus de Rabanales, Universidad de Córdoba, Ed. Marie Curie, 14014 Córdoba, Spain; [email protected] (V.C.); [email protected] (R.E.); [email protected] (F.M.B.); [email protected] (A.A.R.); [email protected] (L.A.-D.); [email protected] (J.H.-C.) 2 Departament de Química and Serveis Tècnics de Recerca, Universitat de Girona, C/M. Aurèlia Campmany, 69, E-17003 Girona, Spain; [email protected] * Correspondence: [email protected]; Tel.: +34-957212065 Abstract: In this work, the covalent immobilization of two ruthenium(II) complexes, II II i.e., [Ru Cl (bpea){(S)(-)(BINAP)}](BF4), 1, and [Ru Cl(bpea)(DPPE)](BF4), 2, where BINAP = 2,2’- bis(diphenylphosphino)-1,1’-binaphthyl and DPPE = 1,2-bis(diphenylphosphino)ethane, have been obtained (AlPO4-Sepiolite@1 and AlPO4-Sepiolite@2) by using a N-tridentate ligand N,N-bis-(2- pyridylmethyl)ethylamine (bpea), linked to an amorphous AlPO4-Sepiolite (20/80) inorganic support. Citation: Caballero, V.; Estevez, R.; This AlPO4-sepiolite support is able to immobilize the double amount of ruthenium complex (1.65%) Luna, D.; Bautista, F.M.; Romero, than the amorphous AlPO4 (0.89%). Both heterogenized complexes have been assessed as catalysts A.A.; Aguado-Deblas, L.; in the liquid phase hydrogenation of several substrates with carbonyl and/or olefinic double bonds Hidalgo-Carrillo, J.; Romero, I.
    [Show full text]
  • Pyrinap Ligands for Enantioselective Syntheses of Amines ✉ Qi Liu1,2,4, Haibo Xu1,2,4, Yuling Li1, Yuan Yao3, Xue Zhang1, Yinlong Guo1 & Shengming Ma 1,3
    ARTICLE https://doi.org/10.1038/s41467-020-20205-0 OPEN Pyrinap ligands for enantioselective syntheses of amines ✉ Qi Liu1,2,4, Haibo Xu1,2,4, Yuling Li1, Yuan Yao3, Xue Zhang1, Yinlong Guo1 & Shengming Ma 1,3 Amines are a class of compounds of essential importance in organic synthesis, pharma- ceuticals and agrochemicals. Due to the importance of chirality in many practical applications of amines, enantioselective syntheses of amines are of high current interest. Here, we wish to R R N R S N 1234567890():,; report the development of ( , a)- -Nap-Pyrinap and ( , a)- -Nap-Pyrinap ligands working with CuBr to catalyze the enantioselective A3-coupling of terminal alkynes, aldehydes, and amines affording optically active propargylic amines, which are platform molecules for the effective derivatization to different chiral amines. With a catalyst loading as low as 0.1 mol% even in gram scale reactions, this protocol is applied to the late stage modification of some drug molecules with highly sensitive functionalities and the asymmetric synthesis of the tubulin polymerization inhibitor (S)-(-)-N-acetylcolchinol in four steps. Mechanistic studies reveal that, unlike reported catalysts, a monomeric copper(I) complex bearing a single chiral ligand is involved in the enantioselectivity-determining step. 1 State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, 200032 Shanghai, People’s Republic of China. 2 University of Chinese Academy of Sciences, 100049 Beijing, People’s Republic of China. 3 Research Center for Molecular Recognition and Synthesis, Department of Chemistry, Fudan University, 220 Handan Road, 200433 Shanghai, People’s Republic of China.
    [Show full text]
  • ACS Style Guide
    ➤ ➤ ➤ ➤ ➤ The ACS Style Guide ➤ ➤ ➤ ➤ ➤ THIRD EDITION The ACS Style Guide Effective Communication of Scientific Information Anne M. Coghill Lorrin R. Garson Editors AMERICAN CHEMICAL SOCIETY Washington, DC OXFORD UNIVERSITY PRESS New York Oxford 2006 Oxford University Press Oxford New York Athens Auckland Bangkok Bogotá Buenos Aires Calcutta Cape Town Chennai Dar es Salaam Delhi Florence Hong Kong Istanbul Karachi Kuala Lumpur Madrid Melbourne Mexico City Mumbai Nairobi Paris São Paulo Singapore Taipei Tokyo Toronto Warsaw and associated companies in Berlin Idaban Copyright © 2006 by the American Chemical Society, Washington, DC Developed and distributed in partnership by the American Chemical Society and Oxford University Press Published by Oxford University Press, Inc. 198 Madison Avenue, New York, NY 10016 Oxford is a registered trademark of Oxford University Press All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, mechanical, photocopying, recording, or otherwise, without the prior permission of the American Chemical Society. Library of Congress Cataloging-in-Publication Data The ACS style guide : effective communication of scientific information.—3rd ed. / Anne M. Coghill [and] Lorrin R. Garson, editors. p. cm. Includes bibliographical references and index. ISBN-13: 978-0-8412-3999-9 (cloth : alk. paper) 1. Chemical literature—Authorship—Handbooks, manuals, etc. 2. Scientific literature— Authorship—Handbooks, manuals, etc. 3. English language—Style—Handbooks, manuals, etc. 4. Authorship—Style manuals. I. Coghill, Anne M. II. Garson, Lorrin R. III. American Chemical Society QD8.5.A25 2006 808'.06654—dc22 2006040668 1 3 5 7 9 8 6 4 2 Printed in the United States of America on acid-free paper ➤ ➤ ➤ ➤ ➤ Contents Foreword.
    [Show full text]
  • Aryl–Fluoride Bond-Forming Reductive Elimination from Nickel(IV) Centers Elizabeth A
    Aryl–Fluoride Bond-Forming Reductive Elimination from Nickel(IV) Centers Elizabeth A. Meucci, † Alireza Ariafard,¥ Allan J. Canty,¥ Jeff W. Kampf, † and Melanie S. Sanford†,* †Department of Chemistry, University of Michigan, 930 N University Ave, Ann Arbor, MI 48109, USA ¥School of Natural Sciences – Chemistry, University of Tasmania, Hobart, Tasmania 7001, Australia ABSTRACT: The treatment of pyridine- and pyrazole-ligated NiII !-aryl complexes with Selectfluor results in C(sp2)– F bond formation under mild conditions. With appropriate design of supporting ligands, diamagnetic NiIV !-aryl fluoride intermediates can be detected spectroscopically and/or isolated during these transformations. These studies demonstrate for the first time that NiIV !-aryl fluoride complexes participate in challenging C(sp2)–F bond-forming reductive elimi- nation to yield aryl fluoride products. Supporting Information Placeholder INTRODUCTION A more recent advance in the field of Ni-mediated Over the past decade, there has been significant pro- fluorination came in a 2012 report by Ritter and cowork- gress in the development of Pd, Cu, and Ag-mediated/cat- ers demonstrating oxidatively-induced aryl–F and aryl– alyzed methods for the formation of aryl-fluoride 18F coupling reactions of NiII(!-aryl) complexes.16 These bonds.1,2 These protocols are finding increasing applica- transformations were proposed to proceed via high-valent tion in the synthesis of fluorine-containing pharmaceuti- Ni intermediates. However, the structures and oxidation cal candidates3 as well as 18F-labelled radiotracers.4 Given states (NiIII versus NiIV) of these species were not identi- that the C(sp2)–F bond-formation is typically the most fied in the original report.
    [Show full text]
  • Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents As the Cross-Coupling Partners
    catalysts Review Pd-Catalyzed Mizoroki-Heck Reactions Using Fluorine-Containing Agents as the Cross-Coupling Partners Jing Yang 1, Hua-Wen Zhao 1,*, Jian He 1 and Cheng-Pan Zhang 1,2,* ID 1 Department of Chemistry, College of Pharmacy, Army Medical University, Shapingba, Chongqing 400038, China; [email protected] (J.Y.); [email protected] (J.H.) 2 School of Chemistry, Chemical Engineering and Life Science, Wuhan University of Technology, 205 Luoshi Road, Wuhan 430070, China * Correspondence: [email protected] (H.-W.Z.); [email protected] (C.-P.Z.); Tel.: +86-023-6877-2357 (H.-W.Z. & C.-P.Z.) Received: 27 December 2017; Accepted: 10 January 2018; Published: 14 January 2018 Abstract: The Mizoroki-Heck reaction represents one of the most convenient methods for carbon-carbon double bond formation in the synthesis of small organic molecules, natural products, pharmaceuticals, agrochemicals, and functional materials. Fluorine-containing organic compounds have found wide applications in the research areas of materials and life sciences over the past several decades. The incorporation of fluorine-containing segments into the target molecules by the Mizoroki-Heck reactions is highly attractive, as these reactions efficiently construct carbon-carbon double bonds bearing fluorinated functional groups by simple procedures. This review summarizes the palladium-catalyzed Mizoroki-Heck reactions using various fluorine-containing reagents as the cross-coupling partners. The first part of the review describes the Pd-catalyzed Mizoroki-Heck reactions of aryl halides or pseudo-halides with the fluorinated alkenes, and the second part discusses the Pd-catalyzed Mizoroki-Heck reactions of the fluorinated halides or pseudo-halides with alkenes.
    [Show full text]
  • Nomenclature of Inorganic Chemistry (IUPAC Recommendations 2005)
    NOMENCLATURE OF INORGANIC CHEMISTRY IUPAC Recommendations 2005 IUPAC Periodic Table of the Elements 118 1 2 21314151617 H He 3 4 5 6 7 8 9 10 Li Be B C N O F Ne 11 12 13 14 15 16 17 18 3456 78910 11 12 Na Mg Al Si P S Cl Ar 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe 55 56 * 57− 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 Cs Ba lanthanoids Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn 87 88 ‡ 89− 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 Fr Ra actinoids Rf Db Sg Bh Hs Mt Ds Rg Uub Uut Uuq Uup Uuh Uus Uuo * 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu ‡ 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr International Union of Pure and Applied Chemistry Nomenclature of Inorganic Chemistry IUPAC RECOMMENDATIONS 2005 Issued by the Division of Chemical Nomenclature and Structure Representation in collaboration with the Division of Inorganic Chemistry Prepared for publication by Neil G.
    [Show full text]
  • Introduction of Fluorine and Fluorine- Containing Functional Groups
    Introduction of Fluorine and Fluorine- Containing Functional Groups The Harvard community has made this article openly available. Please share how this access benefits you. Your story matters Citation Liang, Theresa, Constanze N. Neumann, and Tobias Ritter. 2013. Introduction of Fluorine and Fluorine-Containing Functional Groups. Angewandte Chemie International Edition 52, no. 32: 8214–8264. Published Version doi:10.1002/anie.201206566 Citable link http://nrs.harvard.edu/urn-3:HUL.InstRepos:12336403 Terms of Use This article was downloaded from Harvard University’s DASH repository, and is made available under the terms and conditions applicable to Open Access Policy Articles, as set forth at http:// nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of- use#OAP Fluorine DOI: 10.1002/anie.200((will be filled in by the editorial staff)) Introduction of Fluorine and Fluorine-Containing Functional Groups Theresa Liang, Constanze N. Neumann, and Tobias Ritter* Keywords: C–H functionalization fluorine catalysis trifluoromethylation transition metals 1 Theresa was born in 1985 in San Jose, A few decades ago, the development of several fluorinating California and received her undergraduate reagents such as Selectfluor®[11] and DAST (diethylaminosulfur education at University of California, [12] Berkeley pursuing research under the trifluoride) resulted in fast development of new fluorination mentorship of Prof. Richmond Sarpong in methods. Within the past ten years, a similar leap in fluorination total synthesis. After UC Berkeley, she chemistry has occurred, which we ascribe to increased efforts moved from sunny California to Harvard towards catalytic methods for fluorine incorporation. The merger of University and obtained her PhD in 2012 fluorination chemistry and synthetic organic chemistry––considered working with Prof.
    [Show full text]
  • Organometallic Chemistry
    Chem 4571 Organometallic Chemistry Lecture Notes Prof. George G. Stanley Department of Chemistry Louisiana State University 614 Choppin Hall 578-3471 E-Mail: [email protected] Spring, 2006 (updated 1/15/2006) Class A, B, & C oxidative addition substrate labels dropped. Some new, clearer mechanisms in hydrogenation and hydroformylation chapters. New material added to polymerization chapter (metathesis polymerization, late TM polymerization). New chapter on Pd-catalyzed coupling rxns (by Prof. Lionel Delaude, University of Liege in Belgium). Intro 2 Chemistry 4571 - Organometallic Chemistry (Sp 2006) Prof. George G. Stanley (office: Choppin 614, phone: 578-3471) E-Mail: [email protected] Tuesday - Thursday Lecture 9:10 AM - 10:30 AM Williams 103 This is an advanced undergraduate, introductory graduate level course that covers the organometallic chemistry of the transition metals with emphasis on basic reaction types and the natural extensions to the very relevant area of homogeneous (and heterogeneous) catalysis. An outline of the course contents is shown below: A. Ligand Systems and Electron Counting 1. Oxidation States, d electron configurations, 18-electron "rule" 2. Carbonyls, Phosphines & Hydrides 3. σ bound carbon ligands: alkyls, aryls 4. σ/π-bonded carbon ligands: carbenes, carbynes 5. π-bonded carbon ligands: allyl, cyclobutadiene, cyclopentadienyl, arenes. B. Fundamental Reactions 1. Ligand substitutions 2. Oxidative addition/Reductive elimination 3. Intramolecular insertions/eliminations [4. Nucleophillic/Electrophillic attacks on coordinated ligands (brief coverage, if any)] C. Catalytic Processes 1. Hydrogenation: symmetric and asymmetric 2. Carbonylations: hydroformylation and the Monsanto Acetic Acid Process 3. Polymerization/oligomerization/cyclizations Web Site: chemistry.lsu.edu/stanley/teaching-stanley.htm. Class materials will be posted on the web.
    [Show full text]
  • Structural Consideration BINAP
    | 1 1 BINAP Takeshi Ohkuma and Nobuhito Kurono 1.1 Introduction: Structural Consideration BINAP (2,2u-diphenylphosphino-1,1u-binaphthyl), which was devised by Ryoji Noyori (winner of the Nobel Prize in Chemistry 2001), is typical among chiral diphosphine ligands [1–3]. BINAP chemistry has contributed notably the devel- opment of the field of asymmetric catalysis [1, 4]. This ligand with transition metallic elements forms C2-symmetric chelate complexes. Figure 1.1 indicates the chiral structure created by an (R)-BINAP–transition metal complex. The naph- thalene rings of BINAP are omitted in the side view (right-hand side) for clarity. As illustrated in the top view, the axial-chirality information of the binaphthyl back- bone is transferred through the P-phenyl rings to the four coordination sites shown by & and ’. The coordination sites & placed in the P1–M–P2 plane are sterically influenced by the “equatorial” phenyl rings, whereas the out-of-plane coordination sites, ’, are affected by the “axial” phenyl groups (side view). Con- sequently, the two kinds of quadrant of the chiral structure (first and third versus second and forth in the side view) are clearly discriminated spatially, where the second and fourth quadrants are sterically crowded, while the first and third ones are open for approach of substrates and reagents. This chiral structure realizes excellent enantiodifferentiation in various asymmetric catalytic reactions. The flexibility of the binaphthyl backbone appears to enable a wide scope of substrate. The great success of BINAP chemistry has encouraged researchers to develop BINAP derivatives and related chiral biaryl diphosphines [5]. Figure 1.2 illustrates representative examples.
    [Show full text]
  • Synthesis of Azulenes Via the -Halo Diazo Ketone Strategy
    ANNULATION STRATEGIES FOR THE SYNTHESIS OF AZULENES AND POLYCYCLIC NITROGEN HETEROCYCLES By Aimee Lynn Crombie B.S., Chemistry University of Pittsburgh, 1999 SUBMITTED TO THE DEPARTMENT OF CHEMISTRY IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY at the MASSACHUSETTS INSTITUTE OF TECHNOLOGY June 2004 © 2004 Massachusetts Institute of Technology All Rights Reserved Signatureof Author.. ........................................................................... Department of Chemistry May 12, 2004 Certifiedby .............. ..... ............................................. Rick L. Danheiser Thesis Supervisor A ccepted by ........ ... .../ .... ........................................................... Robert W. Field Departmental Committee on Graduate Studies MASSACHUSMS INSTI iI OF TECHNOLOGY SCIENCE I LI a lnnL I JUN L o uul LIBRARIES 1 This doctoral thesis has been examined by a committee of the Department of Chemistry as follows: ProfessorTimothy F. Jamison........ ..... .. ................................ Chairman Professor Rick L. Danheiser .......... ..... .................... Thesis Supervisor Professor Timothy M. Swager........... ...... 2 Acknowledgments I would first like to thank my advisor, Rick Danheiser. I am grateful for having the opportunity to be a member of his outstanding research group. Rick has been a wonderful mentor and teacher throughout my five years at MIT. I greatly appreciate his persistent efforts to help develop my skills as a chemist and my ability to communicate scientific knowledge. I would also like to thank Rick for all of the time and effort that he devoted to the completion of this thesis. I am grateful to Professor Timothy Jamison and Professor Timothy Swager for their helpful suggestions and comments pertaining to this thesis. I would like to thank Tim Jamison for his support and useful advice throughout my time at MIT. I would not have had the opportunity to enter the Ph.D.
    [Show full text]
  • Chapter 1. Air-Stable Chiral BINAP-Based Phosphines
    Synthesis of Fluorescent Phosphorus Ligands and their Applications in Medical Imaging and Catalysis Jennifer Fairbairn Wallis Engineering Doctorate in Biopharmaceutical Process Development Supervisor of Research: Dr Lee J. Higham Industry Sponsor: High Force Research School of Chemical Engineering – Newcastle University June 2018 Abstract This thesis reports the synthesis of novel, air-stable, fluorescent phosphorus-containing compounds, based on a Bodipy backbone, and their applications in cell imaging and catalysis. The syntheses of all the novel target compounds reported in this thesis are via a primary phosphine, an under-utilised class of compound due to a hazardous reputation. Chapter 1 explores the stability of primary phosphines, how they can be made user-friendly and the ability to create a library of novel phosphorus compounds via the phosphorus-hydrogen bonds. The LJH group synthesised the first, air-stable, fluorescent primary phosphine and Chapter 2 explores a second generation of this type of ligand with an increased fluorescent quantum yield due to the addition of alkyne groups on the boron atom. Chapter 3 details the coordination chemistry of primary phosphines to group 6 and 8 transition metals. Interestingly, the addition of the metals had different effects on the photophysical properties, group 6 metal complexes retained high quantum yields, whereas group 8 metals quenched the fluorescence, possibly due to the heavy atom effect. Chapter 4 discusses the synthesis of fluorescent phosphonium salts which have the potential to be used as trifunctional imaging agents. The three functions within the compounds include i) a fluorophore, to provide in vitro fluorescence imaging, ii) a positive charge on the phosphorus atom to introduce organelle specificity – in this case, to the mitochondria and iii) the inclusion of an 18F radioisotope enables in vivo imaging techniques such as PET imaging.
    [Show full text]