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Enantioselective Reaction Catalyzed by Chiral Cationic Silicon Lewis Acids

Research Project

Project/Area Number 18550097
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka City University

Principal Investigator

HATANAKA Yasuo  Osaka City University, Department of Applied Chemistry, Graduate School of Engineering, 教授 (80344117)

Co-Investigator(Kenkyū-buntansha) 南 達哉  大阪市立大学, 大学院・工学研究科, 准教授 (70251931)
Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥4,120,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥420,000)
Fiscal Year 2007: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2006: ¥2,300,000 (Direct Cost: ¥2,300,000)
KeywordsAsymmetric Diels-Alder Reaction / Chiral Silicon Lewis Acid / Enantioselective Silicon Catalyst / Cationic Silicon Compound / 有機化学 / 合成化学 / 触媒・化学プロセス / ケイ素触媒 / シリルカチオン
Research Abstract

The possibility that silicon might serve as a useful Lewis acid catalyst for asymmetric synthesis has long captured the imagination of organic chemist. We have studied asymmetric Diels-Alder reactions catalyzed by a chiral silicon Lewis acid having (R)-(+)-binaphthol (R-BINOL). In the presence of chiral silicon catalyst having unsabstituted R-BINOL, 3-acyl-1,3-oxazolidin-2-one smoothly reacted with cyclopentadiene to afford the endo Diels-Alder adduct in high yield with moderate enantiomeric excess (at-78℃ for 6h, 87% yield, endo/exo=98/2, (2S)-Diels-Alder adduct=69% ee/endo). Enantioselectivity was found to depend strongly on the size of both the substituents on 3,3'-position of the BINOL ligands and the substituents on the silicon atom. Thus, when the silicon catalyst having (R)-3,3'-dibromo-binaphthol was used, enantioselectivity was reversed and endo adduct with opposite absolute configuration (2R) was obtained (61% ee, endo/exo=98/2). Furthermore, enantioselectivities increased wi … More th the steric bulk of the aryl substituents on 3,3'-position of the BINOL ligands. When the reaction of 3-acyl-1,3-oxazolidin-2-one with cyclopentadiene was conducted by using silicon Lewis acid catalyst bearing (R)-3,3'-bis(4-(2-naphthyl)phenyl)binaphthol, the corresponding Diels-Alder adduct was obtained with 91% ee (2R). The size of substituents on the silicon atom also exerts a strong influence to the enantioselectivity. For example, enantiomeric excess of the product was greatly improved to 99% ee when silicon catalyst having phenyl group on the silicon and (R)-3,3'-bis(4-(2-naphthyl)phenyl)binaphthol ligand was used as the catalyst.
Under the optimized reaction conditions, chiral silyltriflimides (Si-NTf2) bearing (R)-BINOL ligands also effectively catalyzed the enantioselective Diels-Alder reaction of alkenoyl-1,3-oxazolidin-2-ones with cyclohexabutadiene and linear 1,3-dienes to give corresponding Diels-Alder adducts in high yields with high enantioselctivity (up to 98% ee). Catalyst loadings as low as 2.5mol% were enough to complete the reaction. Si29-NMR studies revealed that five-coordinate silicon species formed by the coordination with dienophiles are involved in transition state of the reaction. Less

Report

(3 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • Research Products

    (40 results)

All 2009 2008 2007 Other

All Presentation (39 results) Remarks (1 results)

  • [Presentation] N-ヘテロ環カルベン配位子をもつベーター水素を有するホスファパラダサイクルを用いるアミノ化反応2009

    • Author(s)
      南達哉、佐藤光哉、河村宅哉、畠中康夫
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      千葉
    • Year and Date
      2009-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] In(Otf)3触媒によるケイ素エノラートのアルキンへの付加反応2009

    • Author(s)
      畠中康夫、関英子、津田昭平、南達哉
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      千葉
    • Year and Date
      2009-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] ・キラルなケイ素ルイス酸による触媒的不斉Diels-Alder反応2009

    • Author(s)
      畠中康夫、岩出優樹、阪口祐介、南達哉
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      千葉
    • Year and Date
      2009-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 1級ホスフィンのC-Pカップリング反応を用いた1-ホスファ-2,3-ブタジエン誘導体の合成およびその[4+2]環化付加反応2009

    • Author(s)
      南達哉、岡本紘樹、伊田未加、畠中康夫
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      千葉
    • Year and Date
      2009-03-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] キラルなスルホニルアミド触媒によるシロキシフランの不斉アルドール反応2009

    • Author(s)
      畠中康夫、広瀬大智、松村裕史、南達哉
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      千葉
    • Year and Date
      2009-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Soft Lewis Acids Catalyzed Silylation and Addition Reactions of Terminal Alkyne Using Enolsilanes2008

    • Author(s)
      畠中康夫、関英子、津田昭平、南達哉
    • Organizer
      55th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      大阪
    • Year and Date
      2008-09-30
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Soft Lewis Acids Catalyzed Silylation and Addition Reactions of Terminal Alkyne Using Enolsilanes2008

    • Author(s)
      Yasuo Hatanaka, Eiko Seki, Shouhei Tsuda, Tatsuya Minami
    • Organizer
      55th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      Osaka
    • Year and Date
      2008-09-30
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] New Palladacycles Possesing beta-hydrogen Synthesized by Alkoxypalladation of o-Styrylphosphine as Catalyst in Cross-Coupling Reaction2008

    • Author(s)
      南達哉、川村宅哉、佐藤光也、畠中康夫
    • Organizer
      55th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      大阪
    • Year and Date
      2008-09-29
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] New Palladacycles Possesing beta-hydrogen Synthesized by Alkoxypalladation of o-Styrylphosphine as Catalyst in Cross-Coupling Reaction2008

    • Author(s)
      Tastuya Minami, Takuya Kawamura, Mitsuya Sato, Yasuo Hatanaka
    • Organizer
      55th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      Osaka
    • Year and Date
      2008-09-29
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral Silicon Lewis Acid2008

    • Author(s)
      畠中康夫、岩出優樹、倉田哲夫、南達哉
    • Organizer
      The 15^<th> International Symposium on Organometallic Chemistry
    • Place of Presentation
      大韓民国
    • Year and Date
      2008-07-01
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral Silicon Lewis Acid2008

    • Author(s)
      Yasuo Hatanaka, Yuiki Iwade, Tetsuya Kurata, Tatsuya Minami
    • Organizer
      The 15^<th> International Symposium on Organometallic Chemistry
    • Place of Presentation
      Korea
    • Year and Date
      2008-07-01
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] スチリルホスフィンのアルコキシパラデーションによるβ-水素をもつパラダサイクルの合成と触媒反応への応用2008

    • Author(s)
      南達哉、河村宅哉、畠中康夫
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] ・キラルなケイ素ルイス酸による触媒的不斉Diels-Alder反応2008

    • Author(s)
      畠中康夫、倉田哲夫、南達哉
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2008-03-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral silicon Lewis Acids2008

    • Author(s)
      Yasuo Hatanaka, Tetsuo Kurata, Tatsuya Minami
    • Organizer
      The 87^<th> Annual Meetingof the Chemical Society of Japan
    • Place of Presentation
      Osaka
    • Year and Date
      2008-03-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 0-スチリルボスフィンのアルコキシパラデーションによるβ-水素をもつパラダサイクルの合成と触媒反応への応用2008

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] MAO/HNTf2触媒によるDiels-Alder反応2008

    • Author(s)
      西川真治、畠中康夫、南達哉
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] MAO/HNTf2触媒によるDiels-Alder反応2008

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] ・インジウム触媒による末端アルキンのシリル化反応2008

    • Author(s)
      畠中康夫、松本昭一、南達哉
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2008-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] オルト位にイオウ原子を含む置換基のフェロセニルホスファアルケンのアルコキシパラデーションP-S-Cピンサー型パラジウム錯体の合成2008

    • Author(s)
      南達哉、猪谷圭範、畠中康夫
    • Organizer
      日本化学会第87春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2008-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Silylation of Terminal Alkynes Catalyzed by In(OTf)32008

    • Author(s)
      Yasuo Hatanaka, Shouichi Matsumoto, Tatsuya Minami
    • Organizer
      The 87^<th> Annual Meetingof the Chemical Society of Japan
    • Place of Presentation
      Osaka
    • Year and Date
      2008-03-26
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral Silicon Lewis Acids2007

    • Author(s)
      岩出優樹、倉田哲夫、南達哉、畠中康夫
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      広島
    • Year and Date
      2007-10-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Stereoselective Synthesis of P-C-S Pincer Ligand Coordinated PdComplexes by Alkoxypalladation of Ferrocenylphosphaalkenes2007

    • Author(s)
      南達哉、猪谷圭範、山崎淳二、畠中康夫
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      広島
    • Year and Date
      2007-10-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral Silicon Lewis Acids2007

    • Author(s)
      Yuuki Iwade, Yasuo Hatanaka, Tetsuo Kurata, Tatsuya Minami
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      Hiroshima
    • Year and Date
      2007-10-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] "Stereoselective Synthesis of P-C-S Pincer Ligand Coordinated Pd Complexes by Alkoxypalladation of Ferrocenylphosphaalkenes" Ferrocenylphosphaalkenes 54th Symposium on Organo-metallic Chemistry, Japan, Acids2007

    • Author(s)
      Tatsuya Minami, Takuya Kawamura, Yasuo Hatanaka
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      Hiroshima
    • Year and Date
      2007-10-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Enantioselective Diels-Alder Reaction Catalyzed by Chiral Silicon Lewis Acids,2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-28
    • Related Report
      2007 Annual Research Report
  • [Presentation] Stereoselective Synthesis of P-C-S Pincer Ligand Coordinated Pd Complexes by Alkoxypalladation of Ferrocenylphosphaalkcenes2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      54th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      広島大学
    • Year and Date
      2007-10-27
    • Related Report
      2007 Annual Research Report
  • [Presentation] Stereoselective Synthesis of P-C-S Pincer Ligand Coordinated Pd Complexes by Alkoxypalladation of Ferrocenylphosphaalkenes2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara Centennial Hall
    • Year and Date
      2007-08-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] Nucleophilic Addition of Thiolate Anion to Tricarbonylchromium-Coordinated Arylpkosphsalkenes.2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Towards Onganic Synthesis
    • Place of Presentation
      Nara Centemial Hall
    • Year and Date
      2007-08-05
    • Related Report
      2007 Annual Research Report
  • [Presentation] Nucleophilic Addition of Thiolate Anion to Tricarbonylchromium-Coordinated Arylphospaalkanes2007

    • Author(s)
      南達哉、岸直人、川北佐代子、畠中康夫
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      奈良
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Silylation of Terminal Alkynes Catalyzed by Indium Catalysts : An Efficient Way to Preparation of Alkynylsilane2007

    • Author(s)
      松本昭一、関英子、南達哉、畠中康夫
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      奈良
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Stereoselective Synthesis of P-C-S Pincer Coordinating Palladium Conpmlexes by Alkoxypalladation of Chiral Aryl- and Ferrocenylphosphaalkenes2007

    • Author(s)
      Tatsuya Minami, Yoshinori Itani, Junji Yamazaki, Takuya Kawamura, Yasuo Hatanaka
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      Nara
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Nucleophilic Addition of Thiolate Anion to Tricarbonylchromium-Coordinated Arylphospaalkanes2007

    • Author(s)
      Tatsuya Minami, Naoto Kishi, Sayoko Kawakita, Yasuo Hatanaka
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      Nara
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Silylation of Terminal Alkynes Catalyzed by Indium Catalysts : An Efficient Way to Preparation of Alkynylsilanes2007

    • Author(s)
      Shouichi Matsumoto, Eiko Seki, Ttatsuya Minami, Yasuo Hatanaka
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      Nara
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Highly Enantioselective Silicon Lewis Acid Catalysts2007

    • Author(s)
      岩出優樹、倉田哲夫、畠中康夫、南達哉
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      奈良
    • Year and Date
      2007-08-03
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Stereoselective Synthesis of P-C-S Pincer Coordinating Palladium Conpmlexes by Alkoxypalladation of Chiral Aryl- and Ferrocenylphosphaalkene2007

    • Author(s)
      南達哉、猪谷圭範、山崎淳二、畠中康夫
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      奈良
    • Year and Date
      2007-08-03
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Silicon Triflimides-Catalyzed Asymmetric Diels-Alder Reaction : Highly Enantioselective Silicon Lewis Acid Catalysts2007

    • Author(s)
      Yuhki Iwade, Tetsuo Kurata, Tatsuya minami, Yasuo Hatanaka
    • Organizer
      14^<th> IUPAC Organometallic Chemistry Doected Towards Organic Synthesis
    • Place of Presentation
      Nara
    • Year and Date
      2007-08-03
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Silicon Triflimide-Catalyzed Asymmetric Diels-Alder Reaction:Highly Enantioselective Silicon Lewis Acid Catalysts2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Place of Presentation
      Nara Centennial Hall
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Silylation of Terminal Alkynes Catalyzed by Indium Catalyst:An Efficient Way to Preparation of Alkynylsilanes.2007

    • Author(s)
      畠中 康夫, 南 達哉
    • Organizer
      14th IUPAC Symposium on Organometallic Chemistry Directed Tbwards Organic Synthesis
    • Place of Presentation
      Nara Centennial Hall
    • Year and Date
      2007-08-03
    • Related Report
      2007 Annual Research Report
  • [Presentation] Diels-Alder Reaction Catalyzed byMAO/HNTf2 Lewis Acid2007

    • Author(s)
      Shinji Nishikawa, Yasuo Hatanaka, Tatsuya minami
    • Organizer
      The 89^<th> Annual Meeting of the Chemical Society of Japan
    • Place of Presentation
      Tokyo
    • Year and Date
      2007-03-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Remarks] 「研究成果報告書概要(和文)」より

    • URL

      http://www.eng.osaka-cu.ac.jp/ichiran/G60Hatanaka.pdf

    • Related Report
      2007 Final Research Report Summary

URL: 

Published: 2006-04-01   Modified: 2016-04-21  

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