DOCSLIB.ORG

Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Education and Appointment Awards (selected) 1938 Born, Sep. 3 1993 Tetrahedron Prize (UK) 1967 Ph.D., Hitoshi Nozaki, Kyoto University 1997 Arthur C. Cope Award (ACS) 1968 Associate Professor, Nagoya University 1998 Person of Cartural Merit (Japan) PPh2 1969 Post-doc, E. J. Corey, Hervard University 1999 King Faisal International Prize PPh 1972 Full Professor, Nagoya University for Science (Saudi Arabia) 2 2003 University Professor, Nagoya University 2000 The Order of Culture (Japan) 2003 President, RIKEN 2001 Wolf Prize in Chemistry (Israel) 2015-present Director-General, Center for Research 2001 Roger Adams Award (ACS) and Development Strategy 2001 Nobel Prize in Chemistry (Sweden) Hisashi Yamamoto Kazuhiro Takai Tamejiro Hiyama R Ph Ph O NiCl2 R O X CrCl O CrCl OH O X 2 X X 2 N S R R Al O O S R H H X R H R R Ph V Ph O Ph O S N S [CrIII] R X Pd0 Ph O Si X H [CrIII] F- R Koichiro Oshima Keiji Maruoka Today”s topic Me Me F · His supervised work. O Me B Me H 2 F Sn Sn · Works before the asymmetric hydrogenation Me F Me reaction Me Me Me Me · BINAP synthesis and the asymmetric N Br CoCl2(dpph) (3 mol %) hydrogenation reaction Br Me TMSCH2MgCl (2 equiv.) F Ar · Asymmetric transfer hydrogenation reaction [Cobalt catalyzed Ar Heck reaction] F and isomerization reaction F · Miscellenious Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Supervised Work (Ph. D.) Supervised Work (Post-doc) MeO MeO Li SMe COOEt COOEt O SMe 5 steps SMe O + O O 1 (20 mol%) N2 SMe OEt O 25 25 OH 22% ([α] ; +0.065 ) 50% ([α]D ; +0.644 ) Me O D obs obs MeO Hydrolysis Ph Ph Ph Ph MeO O + O CHO N Me O O Me Cu COOEt COOEt Li O OH O Me N 25 25 28% ([α]D obs ; +0.054 ) 28% ([α]D obs; +0.098 ) Ph 1 OH COOH Tetrahedron. Lett. 1966, 43, 5239. OH COO HO Ph3P Ni0 chemistry with highly strained molecules (±) Prostaglandin F CN 2α Ni HO Me COOMe COOMe NC NiII Tetrahedron. Lett. 1970, 11, 311. HO COOMe (12.5 mol %) COOMe R Benzene MeOOC 60 °C, 45h COOMe R CN 89% 11% Ni J. Am. Chem. Soc. 1971, 93, 4948. COOMe NC COOMe Me Me Me Me CN MeOOC COOMe COOMe MeOOC Ni Me COOMe Me Me NC 1 1,3 and ~30%D Me 2 COOMe 2,3 fission D D COOMe 4 ~30%D ~30% D Me 3 D Ni D D COOMe + R MeOOC Me Me Me Me [Hydrogen scrambling] Me Me > 90% D R D D COOMe Me Me Me COOMe NiII II 1,4 and D Ni 2,3 fission COOMe COOMe Tetrahedron Lett. 1978, 19, 4823. J. Am. Chem. Soc. 1971, 93, 5894. Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Iron carbonyl metal complex C-Nucleotide synthesis O O O R1 R1 O 1) Bromination R1 R1 O O 1) Zn/Cu Fe2(CO)9 2) Elimination Br O R1 R1 O Fe2(CO)9 2) OsO4, H2O2 R2 Br Br Br O Br Br R2 3) protection R2 R2 Br Br O R2 R2 O Me Me Me O Me O O Me Me O Me Me O Me CF3COOOH Me Me O Me Me HN NH O OtBu Me Me O O N Me Me O Me HO Me N N O Me O Urea Me Me O Cyclization; 84% 47% 77% 36% O O 2nd Step; 64% 50% 63% 50% Me Me O HO OH 1) Ozonolysis O 2) Wittig reaction Me J. Am. Chem. Soc. 1971, 93, 1272. Me Thiourea Guanidine S NH2 BINOL derived aluminum hydride reagent O HN HN NH N NH O O HO HO O HO O O OH O O O H (S) R Al O OEt THF R HO OH –78 °C, 2h HO OH HO OH Li (S) (~ 3 equiv.) Chemistry of TMSOTf O TMSOTf (1 mol%) O O OH OH OH * O R OTMS O Al Li TMSO TMS TMS Me Me O DCM D O –78° Me H O R · Super mild reaction condition O O 75%, 82% ee 62%, 95% ee 68%, 71% ee · No equiblium between starting O O TMS TMS material and product, which enable + the kinetic controled protection J. Am. Chem. Soc. 1979, 101, 3129. · Applicable to the protection of ketone in the presence of aldehyde Tetrahedron, 1981, 37, 3899. Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Prostaglandins Three component approach for the synthesis of Prostaglandins O Exhibit diverse pharmalogical properties. O More than 450 publications and 5000 1,4-addition O Trap the enolate R analogues have appeared up to 1982 R I O Me PGO H R Me HO Me HO PGO HO HO Difficulty of three component approach Cu O CuO I O MO MO Me O Li fast PGO 2 Me Me PGO PGO OGP PGO OGP PGO PGO J. Am. Chem. Soc. 1973, 95, 7788. Three component synthesis of Prostagladin Me O COOMe COOH O COOMe H HO O O O 1) Dehydroxylation Me 2) reduction Me Dehydro-PGE2 3) Deprotection HO Me OTHP 4) Hydrolysis OH HO THPO THPO HO PGE1 Tetrahedron Lett. 1982, 23, 5563. Cu Me (Bu P) x 4 O MeOOC Prostacyclin OTHP 1O O 2 Pd(PPh3)4 (10 mol%) O O Tetrahedron Lett. 1983, 24, 1187. tBuLi (2 equiv.), CuI (1equiv.) Introduction of Phosphine Me Me nBu P (2.6 equiv.) 4 ligand suppressed the HO enolization of opposite site and Me I Me reduce the use of chiral building O Me O OH block. Me O HO OTHP O (1equiv) OH Ph Ph H O P O O OMe Pyridinium tosylate 97% ee Rh Tetrahedron Lett. 1982, 23, 4057. HO OMe P Ph H O I Me O Ph O ClO O O H 4 I Me (S) Al O OEt O O 27%, 91% ee OH THF 65%, 94% ee HO 97%, 95% ee Li Tetrahedron Lett. 1987, 28, 4719. Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Synthesis of BINAP Ph Ph t Me Me BuLi Ph recrystallization Br P Ph N Me Br Ph Br then Ph2PCl PPh 1 P then LAH PPh2 PPh2 OH 2 Pd Br PPh P PPh2 PPh2 OH neat, 300 °C THF, –95 °C 2 quant. Ph R; 39% >99% ee 78% Ph S; 36% >99% ee J .Am. Chem. Soc. , 1980, 102, 7932. Me BzO COOH Me O Ph 2 O Ph N Mg, then Ph2POCl P Ph recrystallization P Ph HSiCl3, Et3N Me Pd Cl BzO COOH P Ph P Ph 2 O Ph O Ph 1 (–) 2 J. Org. Chem 1986, 51, 629. Rh catalyzed hydrogenation of olefin Ru catalyzed hydrogenation Ph Ph Ph H OH 4 (< 1 mol %) OH 3 (1 mol %) Ph P 1 1 P H L R COOR H (4 atm) R COOR OMe R1 2 R1 2 Rh Ru L OMe P R2 NHBz EtOH, r.t. R2 NHBz P R2 R2 48h Ph H Ph Ph Ph ClO4 Me Me Me Me Me Me OH Me OH Me OH Me COOH COOH COOMe COOH 99%, 98% ee (from E olefin) 99%, 98% ee (from Z olefin) 96%, 92% ee (from E olefin) NHBz NHBz Me NHBz TBSO Me NHBz Me Me Me OH Me 99%, 99 % ee Me OH H from exo-olefin 96%, 96% ee 93%, 87% ee 97%, 98% ee 98%, 93% ee Me (From Z olefin) (From E olefin) (From Z olefin) NH using (R)-TolBINAP 99%, 99% ee (from E olefin) O J. Am. Chem. Soc. 1987, 109, 1597. J .Am. Chem. Soc. , 1980, 102, 7932. 4 (< 1 mol %) O OH OH O OH O H2 Me Me Me Me X X Cl 3, various condition R R Me SEt OEt Me OH Me OH OH OH O 93% ee (R)BINAP 97% ee O less than 70 % ee OH O O OH Me Me OMe Me Me NMe Chem. Lett. 1985, 14, 1007. 92 % ee 96% ee (R)BINAP 96% ee 2 99% ee J. Am. Chem. Soc. 1988, 110, 629. Ryoji Noyori Baran Group Meeting Masato Saito 10/3/20 Mechanism of Ru catalyzed reduction Ligand-Metal bifunctional catalysis Ar Ar P O OH Ci Hetero atom is required for 5 : amine : KOH = 1: 1 : 2 Ru this reduction Cl Me Me P H , alcohol 2 Ar Ar 5 H2N NH2 Phosphine Amine ee (%) (S)-BINAP (S,S)-DPEN 97% (S)-BINAP (R,R)-DPEN 14% DPEN Me OH MeO OH Me OH Me Me OMe Me Me NH2 NH (S)-BINAP/ (S)-TolBINAP/ (S)-XylBINAP/ 2 (S)-DAIPEN (S)-DAIPEN (S)-DAIPEN 90% ee 99% ee 95% ee DAIPEN Catalyst for Base-Free condition · Selective reduction of ketone BH3 O OH Ar Ar H (10 atm) 6 (0.2 mol%) H2 Ph 2 H (S)-BINAP/(S)-DAIPEN H (8 atm) P N 2 O (0.000001 mol%) OH O Me Me Ru i K2CO3 PrOH N P H Ph Me Me Me [without base] H MeOH Ar Ar H 99%, 97% ee 6 quant, 97% ee 0% OH OH O OH · Role of strong base O Me Me N Me Me Me Ar Ar Ar Ar H2 Strong base H2 P Cl P H 99%, 99% de 100%, 94% ee 95%, 99% ee N H2 N Ru Ru J. Am. Chem. Soc. 2002, 124, 6508.
Load more

Recommended publications
  • Studies on Cross-Coupling Reactions Using Trialkylsilyl-Type Reagents
    中央大学博士論文 Studies on Cross-coupling Reactions Using Trialkylsilyl-type Reagents Takeshi Komiyama 小宮山 剛司 博士（工学） 中央大学大学院 理工学研究科 応用化学専攻 平成３０年度 ２０１９年３月 Preface The present dissertation is concerned with cross-coupling reactions using trialkylsilyl-type reagents. The studies described here have been carried out under the guidance of Professor Tamejiro Hiyama at Research and Development Initiative, Chuo University, during April 2013–January 2019. I would like to express my cordial gratitude to Professor Tamejiro Hiyama, who always encouraged me with enthusiasm by showing a variety of possible future research directions. I am deeply grateful to Associate Professor Yasunori Minami for his pertinent encouragements and discussions for the duration of my Ph.D. program. My sincere appreciation is toward Professors Yoichi Ishii, Shin-ichi Fukuzawa, and Haruhiko Fuwa at Department of Applied Chemistry, Chuo University, Professor Mariko Matsunaga at Department of Electrical Electronic and Communication Engineering, Chuo University, and Professor Yoshiaki Nishibayashi at Department of System Innovation, the University of Tokyo for reviewing this thesis and providing me with valuable suggestions. Deep thanks are due to Professor Tomiki Ikeda, Associate Professor Toru Ube, Kazuma Nojima, and Yuto Yanahashi for assistance of polymer analysis. I also thank Professor Makoto Yamashita and Assistant Professor Katsunori Suzuki for stimulating discussions. All members in the Hiyama group, Dr. Kenta Shimizu, Yuki Shiraishi, Hirofumi Yoshiyasu, Mayuko Kanda, Kotomi Yamada, Tomohiro Anami, Chisato Tsuruoka, Tatsuro Kodama, Shu-ichi Uno, Megumi Sakai, Yuta Noguchi, Mayu Yamada, Yuki Furuya, and Takumi Sakamaki are appreciated for their friendships, and secretaries, Tomoko Yoshida and Hideko Sekiguchi for their assistances. I am deeply indebted to Professor Martin Oestreich at Technische Universität Berlin for giving me an opportunity to study in Berlin for a month.
    [Show full text]
  • Title Synthetic Studies on the Chemistry of Gem-Dimetalation with Inter-Element Compounds( Dissertation 全文 )
    Synthetic Studies on the Chemistry of gem-Dimetalation with Title Inter-element Compounds( Dissertation_全文 ) Author(s) Kurahashi, Takuya Citation Kyoto University (京都大学) Issue Date 2003-03-24 URL http://dx.doi.org/10.14989/doctor.k10168 Right Type Thesis or Dissertation Textversion author Kyoto University Synthetic Studies on the Chemistry ofgem-Dimetalation with Inter-element Compounds Takuya Kurahashi 2003 Synthetic Studies on the Chemistry ofgem-Dimetalation with Inter-element Compounds Takuya Kurahashi 2003 Contents Chapter 1 Introduction and General Summary 1 Chapter 2 Silylborylation and Diborylation of Alkylidene-type Carbenoids. Synthesis of 1-Boryl-1-silyl-1-alkenes and 1,1-Diboryl-1-alkenes 21 Chapter 3 Stereospecific Silylborylation of a-Chloroallyllithiums. Synthesis and Reactions of Allylic gem-Silylborylated Reagents 53 Chapter 4 Synthesis and Reactions of 1-Silyl-1-borylallenes 81 Chapter 5 Efficient Synthesis of 2,3-Diboryl-1,3-butadiene and Synthetic Applications 95 List ofPublications - 115 Acknowledgments - 117 Abbreviations Ac acetyl J coupling constant in Hz Anal. element analysis LDA lithium diisopropylamide aq. aqueous m multiplet (spectral) Bn benzyl M mol per liter Bpin 4,4,5,5-tetramethyl-I,3,2-dioxabolan-2-yl Me methyl brs broad singlet (spectral) MEM 2-methoxyethoxymethyI Bu butyl min minute(s) calcd calculated mL mililiter cat. catalytic mp melting point Cy cyclohexyl Ms mesyl d doublet (spectral) NMR nuclear magnetic resonance dba dibenzylideneacetone Pent pentyl DME 1,2,-dimethoxyethane Ph phenyl DMF N,N-dimethylformamide
    [Show full text]
  • Activation of the Si−B Interelement Bond: Mechanism, Catalysis, and Synthesis Martin Oestreich,* Eduard Hartmann, and Marius Mewald
    Review pubs.acs.org/CR Activation of the Si−B Interelement Bond: Mechanism, Catalysis, and Synthesis Martin Oestreich,* Eduard Hartmann, and Marius Mewald Institut für Chemie, Technische Universitaẗ Berlin, Strasse des 17. Juni 115, 10623 Berlin, Germany Acknowledgments AL References AL 1. INTRODUCTION Synthetic chemistry is almost unimaginable without three main group elements, namely, boron, silicon, and tin. When attached to a carbon atom of any hybridization, these functional groups serve as exceptionally versatile linchpins in synthesis, selectively transforming into an enormous breadth of C−C and C−Het bonds. Areas such as cross-coupling or classes of reagents such as allylic and propargylic/allenylic metals are largely dominated CONTENTS by these main group elements. The main group element- functionalized intermediate is, however, usually the vehicle to 1. Introduction A arrive at a target molecule without any of these heteroatoms. − 2. Preparation of Si B Compounds B Nevertheless, methods for the formation of bonds between − 3. Mechanisms of Si B Bond Activation D carbon and main group elements, i.e., accessing main group 4. Functionalization of Unsaturated Compounds E element-based compounds, are likewise essential to the overall − 4.1. 1,2-Addition to Isolated C C Multiple Bonds E development of the field. 4.1.1. Alkynes E Interelement compounds, that is, compounds containing an 4.1.2. Alkenes I interelement bond,1 are attractive main group element n − 4.2. 1,2-, 1,4-, and 1, -Addition to C C Multiple- precursors as these provide the opportunity to transfer both Bond Systems K bonding partners to an unsaturated substrate.
    [Show full text]
  • Chemistry of Functional Organic Chemicals
    France-Japan Joint Forum Chemistry of Functional Organic Chemicals International Year of Chemistry – 2011 – 23 - 25 juin 2011 ISIS Université de Strasbourg France-Japan Joint Forum on Chemistry of Functional Organic Chemicals for Celebrating International Year of Chemistry – 2011 – organized by UDS, CNRS and JSPS With the support of: Région Alsace Conseil Général du Bas-Rhin Communauté Urbaine de Strasbourg Consulat Général du Japon à Strasbourg Scientific Coordinators: Jean-Pierre Sauvage, Kazuhiko Saigo Organizers : Jean-Marc Planeix, Yoichi Nakatani, Gilberte Chambaud, Régis Réau, Pascal Breuilles Secretariat: Francine Pinard, Satoko Tada, Bertrand Pinard, Mina Saito Video of the forum is available on Canal U, the web-TV of French Ministry of Higher Education and Research: http://www.canalc2.tv/ Program Timing Schedule Day One – Thursday 23rd June 2011 08:00 Registration Institut de Science et d'Ingénierie Supramoléculaires (ISIS), Université de Strasbourg (UDS) 08:40-09:10 Welcome remarks Chairpersons Jean-Marc Planeix, Yoichi Nakatani - Éric Westhof Vice-President "Recherche et formation doctorale", University of Strasbourg - Hiroshi Karube Consul General of Japan in Strasbourg - Régis Réau Director, Institute of Chemistry, CNRS - Henri Dreyfus Representative of the Mayor of Strasbourg - François Loos Vice-President, Conseil Régional d’Alsace - Kazuhiko Saigo Former Chair, 116th Committee of JSPS Vice-President, Kochi University of Technology - Motoyuki Ono President, Japan Society for the Promotion of Science (JSPS) 09:10-10:40
    [Show full text]
  • 01-Front Page
    CRC International Symposium in Moscow Cross-Coupling & Organometallics Organizers: Zelinsky Institute of Organic Chemistry Russian Academy of Science Hokkaido University, Japan Catalysis Research Center, Hokkaido Univeristy, Japan Co-Organizers: Moscow State University Japan Interaction in Science & Technology Forum (JIST) Sigma-Aldrich Corporation The Chemical Society of Japan, Hokkaido University GCOE Program Hokkaido Branch Catalysis & Materials Science The CRC International Symposium in Moscow Program 09:00 – 10:00 - Registration on the CRC Symposium 10:00 – 10:10 - Opening Ceremony: Tamotsu Takahashi (Hokkaido Univ., Japan) 10:10 – 10:50 Ei-ichi Negishi (Purdue Univ., USA) Transition Metal-Catalyzed C-C Bond Formation: Cross-Coupling and Carbometalation that Have Revolutionized Organic Synthesis 10:50 – 10:55 - Questions/Discussion 10:55 – 11:35 Irina P.Beletskaya (Moscow State Univ., Russia) Some Aspects of Green Chemistry Principles Application to Transition Metal Catalysis 11:35 – 11:40 - Questions/Discussion 11:40 – 12:10 - Coffee-break 1 12:10 – 12:50 Akira Suzuki (Hokkaido Univ., Japan) Cross-Coupling Reactions of Organoboron Compounds 12:50 – 13:00 - Questions/Discussion 13:00 – 15:00 Lunch Poster Presentations 15:00 – 15:40 Yuri Belokon (INEOS RAS, Russia) Binuclear Lewis Acids in Asymmetric Catalysis: Success and Unexpected Problems 15:40 – 15:45 - Questions/Discussion 15:45 – 16:15 - Coffee-break 2 16:15 – 16:55 Paul Knochel (Univ. of Munich, Germany) New Chemoseletive and Regioselective Cross-Couplings with Functionalized Organometallics 16:55 – 17:00 - Questions/Discussion 17:00 – 17:40 Tamejiro Hiyama (Kyoto Univ., Japan) Invention of Transition Metal-Catalyzed Carbon-Carbon Bond Forming Reactions for Organic Synthesis 17:40 – 18:00 - Closing Remarks 19:00 – 21:00 - Gala dinner Plenary Lectures Ei-ichi NEGISHI H.C.
    [Show full text]
  • Silicon Based Cross Coupling Reactions Through Intramolecular Activation
    Silicon ─ Based Cross ─ Coupling Reactions Through Intramolecular Activation Yoshiaki Nakao ＊ and Tamejiro Hiyama ＊＊ ＊ Department of Material Chemistry, Graduate School of Engineering, Kyoto University Kyo＊to＊ University Katsura, Nishikyo ─ ku, Kyoto 615 ─ 8510, Japan Research and Development Initiative, Chuo University 1 ─ 13 ─ 27 Kasuga, Bunkyo ─ ku, Tokyo 112 ─ 8551 (Received July 1, 2011; E ─ mail: [email protected]; [email protected]) Abstract: Tetraorganosilanes having a 2 ─ (hydroxymethyl)phenyl group are found to undergo the silicon ─ based cross ─ coupling reaction. The proximal hydroxy group allows transmetalation of alkyl, alkenyl, and aryl groups on silicon to palladium(II), nickel(II), or copper(I or II) to occur, and hence participation in the cross ─ coupling reaction under mild conditions with excellent chemoselectivity. The high stability of the tetraorganosilicon structure is demonstrated by functionalization under various acidic, basic, and oxidative conditions which leave the silyl group completely intact. Moreover, highly efcient synthesis of functional molecules such as oli- goarenes has been achieved through iterative cross ─ coupling/O ─ deprotection sequences by simply switching reactivity with orthogonal O ─ protection/deprotection. hydroxide to generate pentacoordinate silicates in situ ham- 1． Introduction pered application to the synthesis of highly functionalized tar- Metal ─ catalyzed cross ─ coupling reactions have been devel- get molecules and the manufacture of commodity and spe- oped extensively over the last three decades, and applied widely cialty chemicals. Accordingly, efforts have been made to to synthesis of a number of useful substances ranging from overcome these issues and make the silicon ─ based protocol biologically active compounds such as pharmaceuticals and attractive for synthetic chemists.
    [Show full text]
  • Molecular Activation Directed Toward Straightforward Organic Synthesis
    The 5th China-Japan Young Chemists Forum Molecular Activation Directed toward Straightforward Organic Synthesis The Chemical Society of Japan The 95th Annual Meeting Date March 27th, 2015 Venue Funabashi Campus, Nihon University, Chiba, Japan Welcome Address Welcome to the 5th China-Japan Young Chemists Forum, held at the same venue as the 95th CSJ Annual Meeting, Funabashi Campus, College of Science and Technology, Nihon University, Chiba, Japan on March 27th, 2015, under the co-sponsorship of the Chinese Chemical Society (CCS) and the Chemical Society of Japan (CSJ). The CSJ has a history of 137 years, with a current membership of about 30,000, and is one of the most influential learned societies in Japan, covering most areas of pure and applied chemistry both in academia and industry. Our prime mission is to contribute to social development through advancing science, developing technology, promoting industry, diffusion of knowledge relating to chemistry, and developing human resources. To pursue this mission, the CSJ holds various conferences, such as "the CSJ Annual Meeting" with 8,500 participants every spring, and "CSJ Chemistry Festa" every autumn. This series of bilateral meetings originates from the first one in 2010 held in Xiamen University, followed by the second in 2012 at Sichuan University and the third in 2013 at Ritsumeikan University during the 93rd CSJ Annual Meeting. The fourth Forum was held in 2014 at Peking University during the 29th CCS Annual Meeting “A Molecular Activation Directed toward Straightforward Organic Synthesis”, the topic of the 2015 China-Japan Forum is a highly advanced interdisciplinary field that covers from organotransition metal chemistry to organic synthesis, featuring novel metal complexes that enable activation of unreactive C–H and C–C bonds, catalytic CO2 fixation, novel radical reactions, catalytic C–H and C–O functionalizations and their applications to total synthesis of natural products.
    [Show full text]
  • TCIMAIL No.166 |
    ISSN 1349-4848 number166 CONTENTS 2 Research Article - Invention of Synthetic Reactions Based on σ-Bond Activation Tamejiro Hiyama RDI Professor, Research and Development Initiative, Chuo University 12 New Products Information : cat C E - Nanodiamond C E + - Useful Copper Reagent for Coupling Reactions - Ligands for Click Chemistry E = Si, Sn, CN, H; cat: Ni(0), Pd(0) - Non-detergent Sulfobetaines - Cyclitol No.166 No.166 ResearchResearch ArticleArticle Invention of Synthetic Reactions Based on σ−Bond Activation Tamejiro Hiyama RDI Professor Research and Development Initiative, Chuo University 1. Introduction 2. Organosilicon Reagent/Fluoride Ion During my studies with Professor Hitosi Nozaki, we It would be fascinating if both the cationic and anionic had weekly discussions about the present and future of our species were generated by the cleavage of element–element chemistry. It may have been in the summer of 1980 that bonds. I pictured a reaction scheme in which disilane and a Professor Nozaki said one day “When I gave a lecture in fluoride ion produce a silyl anion and fluorosilane, with the Europe, I asked the audience ‘Do you know a reaction system fluorosilane behaving similar to an electrophilic silyl cation. I that involves both carbanionic and carbocationic species?’ No found that when hexamethyldisilane and tetrabutylammonium one gave me the correct answer.” He then suggested the reaction fluoride (TBAF) are mixed in hexamethylphosophric triamide of allylic acetate with trialkylaluminum, R3Al, whereby an (HMPA) in the presence of an aldehyde, carbonyl attack of the allylic cation and alanate are produced and the alanate delivers trimethylsilyl anion occurs, followed by O-trimethylsilylation.
    [Show full text]
  • Yasuda, Shigeo C
    Studies on Synthesis and Reactions of Title Aryldicarbonylcyclopentadienyliron( Dissertation_全文 ) Author(s) Yasuda, Shigeo Citation 京都大学 Issue Date 2010-03-23 URL https://doi.org/10.14989/doctor.k15387 Right Type Thesis or Dissertation Textversion author Kyoto University Studies on Synthesis and Reactions of Aryldicarbonylcyclopentadienyliron Shigeo Yasuda 2010 Contents General Introduction ------------------------------------------------------------------------------------------1 Chapter 1 Synthesis of Aryliron Complexes by Palladium-Catalyzed Transmetalation between [CpFe(CO)2I] and Aryl Grignard Reagents and Their Chemistry Directed toward Organic Synthesis -------------------------------------------------------------------------------------- 19 Chapter 2 Synthesis of Aryliron Complexes [CpFe(CO)2Ar] by Palladium-Catalyzed Reactions of [CpFe(CO)2I] with Arylzinc, -Boron, or -Indium Reagents ----------------------------------- 37 Chapter 3 Synthesis of Functionalized Aryliron Complexes [CpFe(CO)2Ar] by Copper-Mediated Transmetalation between [CpFe(CO)2I] and Aryltin Reagents ------------- 57 Chapter 4 Use of Aryliron Complexes [CpFe(CO)2Ar] as Arylcarbonyl Cation Equivalents in the Reactions with Organolithium Reagents to Yield Ketones ----------------------------------- 65 Chapter 5 Arylation of Styrenes with Aryliron Complexes [CpFe(CO)2Ar]-------------------------------- 81 Appendix Vanadium-Catalyzed Cross-Coupling Reactions of Alkyl Halides with Aryl Grignard Reagents -------------------------------------------------------------------------------------
    [Show full text]
  • Syntheses and Metal Mediated Reaction Chemistry of 2-Silyl-1,3-Dienes
    SYNTHESES AND METAL MEDIATED REACTION CHEMISTRY OF 2-SILYL-1,3-DIENES BY PARTHA PRATIM CHOUDHURY A Dissertation Submitted to the Graduate Faculty of WAKE FOREST UNIVERSITY GRADUATE SCHOOL OF ARTS AND SCIENCES in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Chemistry August, 2015 Winston-Salem, North Carolina Approved By: Mark E. Welker, Ph.D., Advisor Oana D. Jurchescu, Ph.D., Chair Rebecca W. Alexander, Ph.D. Willie L. Hinze, Ph.D. Amanda C. Jones, Ph.D. ACKNOWLEDGEMENTS The hardest and the sweetest part of the doctoral dissertation is writing the acknowledgement section. Before I make any further comments I must admit the best decision that I have taken till this point of my life is joining the Welker group at the department of chemistry at Wake Forest University. It was the turning point of my life, scientific career, professional and personal development, and intellectual enrichment. I have no words to thank and acknowledge enough my Ph.D. advisor Professor Mark E Welker. He introduced me to the realm of organic chemistry, taught me the subject and the fundamentals, demonstrated how to carry out experiments and how to multitask, always encouraged me to read and think scientifically, provided intellectual support to generate ideas, supported me in all possible and probable ways. We had very exciting discussions on scientific problems, he walked me through knowledge assimilation and application process. He made me an independent researcher and a skilled chemist. He not only served as the Ph.D. advisor but also introduced me to the bigger world and prepared me for the life after Wake Forest University.
    [Show full text]
  • Abramov‐Type Phosphonylation of Aldehydes 389 Acetonitrile 102, 105, 157, 369, 443 Achiral Cyclic Ketones 371 Achiral Methyl K
    533 Index a trialkylsilyl ketene acetals 379–382 Abramov‐type phosphonylation of aliphatic aldehydes 10, 11, 61, 67, 366, aldehydes 389 368, 369, 373, 376, 379, 385–388, acetonitrile 102, 105, 157, 369, 443 391, 395 achiral cyclic ketones 371 alkene hydrosilylation 57, 89–90, 421, achiral methyl ketones 371 429, 431, 432, 450 acid‐catalyzed indole silylation 223 primary and secondary hydrosilanes activated substrate interaction, externally alkoxyhydrosilanes 427 coordinated‐nucleophile hydrosilanes 427 direct aldol addition, of activated monohydrosilylation 427 thioesters 395–396 platinum‐catalyzed hydrosilylation, enantioselective Morita–Baylis– chlorohydrosilanes 427 Hillman reaction 396–397 TOF 428 acyclic nucleophiles 371 alkene isomerization 250, 433 acylhydrazono esters, allylation alkenylsilanes 18, 288, 294, 296, 298, of 361 299, 303, 519, 521 acylsilanes 11 alkenylsilanols 292 adamant‐1‐yl methyl ketone 451 alkenyl[tris(trimethylsilyl)] agostic bis(silyl) hydridorhodium(III) silanes 275 complex 444 alkoxide base‐catalyzed silaboration, of aldehyde‐derived trichlorosilyl enol aromatic alkenes 24 ethers 375 alkoxyhydrosilanes 418–427 aldehydes, allylation of 3, 336, 1‐alkyl‐1’‐arylethylenes 430 362–364, 366, 368, 369, alkyl chloro silyl ether 366, 376 375–378 alkylsilanes 241, 263, 265–267 aldol addition 371–373, 375, 378–386, alkynyltrimethylsilanes 308 391, 393–396 allylacetone 454 aldolization process 371, 373 allylating reagent 366, 376 aldol reactions allylation of aldehydes 3, 336, preformed enoxysilane 362–364, 366, 367, 375–376 derivatives 371–375 allylation, of benzaldehyde 3, 336, trialkylsilyl enol ether 362–364, 366, 368–370, derivatives 378–379 376–378 Organosilicon Chemistry: Novel Approaches and Reactions, First Edition. Edited by Tamejiro Hiyama and Martin Oestreich © 2019 Wiley-VCH Verlag GmbH & Co.
    [Show full text]
  • Tetraorganosilanes for the Practical Cross-Coupling Reaction*
    Pure Appl. Chem., Vol. 78, No. 2, pp. 435–440, 2006. doi:10.1351/pac200678020435 © 2006 IUPAC Alkenyl- and aryl[2-(hydroxymethyl)phenyl]- dimethylsilanes: Tetraorganosilanes for the practical cross-coupling reaction* Yoshiaki Nakao, Akhila K. Sahoo, Hidekazu Imanaka, Akira Yada, and Tamejiro Hiyama‡ Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan Abstract: Readily accessible and highly stable alkenyl- and aryl[2-(hydroxymethyl)- phenyl]dimethylsilanes cross-couple with various aryl and alkenyl halides under mild reac- tion conditions employing K2CO3 as a base at 35–80 °C. The reaction tolerates a diverse range of functional groups including silyl protections. The silicon residue, cyclic silyl ether, is readily recovered and reused on a gram-scale synthesis. Intramolecular coordination of a proximal hydroxyl group is considered to efficiently form pentacoordinated silicates having a transferable group at an axial position. Keywords: cross-coupling; homogeneous catalysis; biaryl; palladium; silicon. INTRODUCTION The metal-catalyzed cross-coupling reaction is now an indispensable tool for modern organic synthesis [1]. Among many cross-coupling protocols, a silicon-based methodology is gaining increasing impor- tance and interest in view that silicon reagents are generally highly stable and nontoxic [2]. In 1988, Hiyama and Hatanaka revealed that readily accessible organo(halo)silanes undergo transmetallation to palladium(II), an oxidative adduct of aryl halides to palladium(0), upon treatment with a fluoride acti- vator to form pentacoordinate silicates, achieving the cross-coupling reaction [3]. Since this discovery, in situ formation of pentacoordinated silicates by use of halosilanes or alkoxysilanes in the presence of a fluoride activator has been a standard strategy in the silicon-based cross-coupling protocol [2].
    [Show full text]