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Asymmetric Synthesis of Highly Functionalized Chiral Silicon Molecules and Application Thereof

Research Project

Project/Area Number 24350048
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

Igawa Kazunobu  九州大学, 先導物質化学研究所, 助教 (80401529)

Project Period (FY) 2012-04-01 – 2016-03-31
Project Status Completed (Fiscal Year 2015)
Budget Amount *help
¥18,200,000 (Direct Cost: ¥14,000,000、Indirect Cost: ¥4,200,000)
Fiscal Year 2015: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2014: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2013: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2012: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Keywords不斉合成 / 有機ケイ素分子 / ケイ素キラリティー / 生理活性 / キラルケイ素分子 / セロトニン受容タンパク / キラルケイ素化合物 / シラシクロペンテントリオール / 生理活性化合物 / エナンチオ選択的β-脱離反応 / 脱水素水和反応 / 立体化学経路 / 不斉ヒドロシリル化 / オゾン酸化
Outline of Final Research Achievements

A variety of novel chiral silicon molecules were synthesized in optically active form by highly enantioselective asymmetric desymmetrization of achiral silicon molecules and further stereoselective transformations. 1) Enantioselective hydrosilylation of dihydrosilanes with a chiral platinum catalyst afforded chiral alkenylhydrosilanes in optically active form up to 86% ee, which were converted into chiral silanols in highly stereoselective manner. 2) Enantioselective beta-elimination of silacyclopentene oxides with a novel chiral lithium amide afforded chiral silacyclopentenols in optically active form up to >98% ee, which were converted in to a variety of chiral silacyclopentane derivatives. One of the synthesized silacyclopentane derivatives showed substantial binding activity to a serotonin receptor protein, in which the silicon chirality is the key structural factor for the binding activity.

Report

(5 results)
  • 2015 Annual Research Report   Final Research Report ( PDF )
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • 2012 Annual Research Report
  • Research Products

    (42 results)

All 2016 2015 2014 2013 2012 Other

All Journal Article (7 results) (of which Peer Reviewed: 7 results,  Acknowledgement Compliant: 3 results) Presentation (34 results) (of which Int'l Joint Research: 1 results,  Invited: 7 results) Book (1 results)

  • [Journal Article] Enantioselective Synthesis of Silacyclopentanes2016

    • Author(s)
      K. Igawa, D. Yoshihiro, Y. Abe, K. Tomooka
    • Journal Title

      Anger. Chem. Int. Ed

      Volume: 55 Issue: 19 Pages: 5814-5818

    • DOI

      10.1002/anie.201511728

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic Enantioselective Synthesis of Planar-Chiral Cyclic Amides Based on a Pd-Catalyzed Asymmetric Allylic Substitution Reaction2015

    • Author(s)
      K. Igawa, N. Ichikawa, Y. Ano, K. Katanoda, M. Ito, T. Akiyama, K. Tomooka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 137 Issue: 23 Pages: 7294-7297

    • DOI

      10.1021/jacs.5b04340

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Structural Analysis of Nine-membered enyne nitrogen Heterocycles2015

    • Author(s)
      K. Igawa, T. Kawabata, K. Uehara, K. Tomooka
    • Journal Title

      HETEROCYCLES

      Volume: 90 Issue: 2 Pages: 901-906

    • DOI

      10.3987/com-14-s(k)109

    • Related Report
      2015 Annual Research Report 2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Planar Chiral Dialkoxysilane: Introduction of Inherent Chirality and High Reactivity in Conventional Achiral Alkene2014

    • Author(s)
      Tomooka, K.; Miyasaka, S.; Motomura, S.; Igawa, K.
    • Journal Title

      Chem. Eur. J.

      Volume: 20 Issue: 25 Pages: 7598-7602

    • DOI

      10.1002/chem.201402434

    • Related Report
      2014 Annual Research Report 2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Ozone Oxidation of Silylalkenes Using a C-2-Symmetrical Dialkoxysilyl Group as a Chiral Auxiliary2014

    • Author(s)
      K. Igawa, Y. Kawasaki, K. Nishino, N. Mitsuda, K. Tomooka
    • Journal Title

      CHEMISTRY-A EUROPEAN JOURNAL

      Volume: 20 Issue: 30 Pages: 9255-9258

    • DOI

      10.1002/chem.201402996

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Oxidation of Silanes to Silanols on Pd Nanoparticles: H2 Desorption Accelerated by Surface Oxygen Atom2013

    • Author(s)
      T. Kamachi, K. Shimizu, D. Yoshihiro, K. Igawa, K. Tomooka, and K. Yoshizawa
    • Journal Title

      J. Phys. Chem. C

      Volume: 117 Issue: 44 Pages: 22967-22973

    • DOI

      10.1021/jp408269s

    • Related Report
      2013 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Enantioselective Synthesis of Alkenylhydrosilanes2012

    • Author(s)
      Igawa, K.; Yoshihiro, D.; Ichikawa, N.; Kokan, N.; Tomooka, K.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 51 Issue: 51 Pages: 12745-12748

    • DOI

      10.1002/anie.201207361

    • Related Report
      2012 Annual Research Report
    • Peer Reviewed
  • [Presentation] キラルシラシクロペンタン類のエナンチオ選択的合成2016

    • Author(s)
      吉廣大佑,安倍雄介,井川和宣,友岡克彦
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学田辺キャンパス,田辺
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] ジアルコキシシランの求核置換反応とその立体化学経路2016

    • Author(s)
      井川和宣,高田純子,重松和樹,友岡克彦
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学田辺キャンパス,田辺
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] キラルケイ素分子の不斉合成とその生物機能の探索2016

    • Author(s)
      井川和宣
    • Organizer
      分子イメージングセミナー
    • Place of Presentation
      理化学研究所ライフサイエンス技術基盤研究センター,神戸
    • Year and Date
      2016-02-09
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] 「ケイ素」と「歪み」を活用する新しいアルキン化学2016

    • Author(s)
      井川和宣
    • Organizer
      第27回触媒化学融合研究センター講演会
    • Place of Presentation
      産業技術総合研究所,つくば
    • Year and Date
      2016-01-15
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] Enantioselective Synthesis of Chiral Silanol and Stereospecific Transformation Thereof2015

    • Author(s)
      Kazunobu Igawa, Junko Takada, Daisuke Yoshihiro, Naoto Kokan, Nobumasa Ichikawa, Tomohiro Shimano, Katsuhiko Tomooka
    • Organizer
      The 13th International Kyoto Conference on New Aspects of Organic Chemistry
    • Place of Presentation
      Right Royal Hotel KYOTO, Kyoto, Japan
    • Year and Date
      2015-11-09
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 特異な反応性と立体化学的特徴を有する有機ケイ素分子の化学2015

    • Author(s)
      井川和宣
    • Organizer
      第19回ケイ素化学協会シンポジウム
    • Place of Presentation
      ラフォーレ琵琶湖,守山
    • Year and Date
      2015-10-23
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] キラルシラシクロペンタン誘導体の不斉合成2015

    • Author(s)
      吉廣大佑,安倍雄介,井川和宣,友岡克彦
    • Organizer
      第19回ケイ素化学協会シンポジウム
    • Place of Presentation
      ラフォーレ琵琶湖,守山
    • Year and Date
      2015-10-23
    • Related Report
      2015 Annual Research Report
  • [Presentation] 多官能基化されたキラルシクロペンタン誘導体の不斉合成2015

    • Author(s)
      吉廣大佑,安倍雄介,井川和宣,友岡克彦
    • Organizer
      第107回有機合成シンポジウム
    • Place of Presentation
      慶応義塾大学薬学部,東京
    • Year and Date
      2015-06-09
    • Related Report
      2015 Annual Research Report
  • [Presentation] シラシクロペンテノールのエナンチオ選択的不斉合成とその変換2015

    • Author(s)
      吉廣大佑,安部雄介,井川和宣,友岡克彦
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] 動的面不斉を有する9員環ジアルコキシシランの合成とその立体化学挙動2015

    • Author(s)
      井川和宣,工藤雄大,本村彰悟,宮坂祥司,友岡克彦
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成とその変換2014

    • Author(s)
      吉廣大佑,市川延雅,古閑直人,井川和宣,友岡克彦
    • Organizer
      第31回有機合成化学セミナー
    • Place of Presentation
      福岡
    • Year and Date
      2014-09-17 – 2014-09-19
    • Related Report
      2014 Annual Research Report
  • [Presentation] 不斉オゾン酸化反応の開発と応用2014

    • Author(s)
      河崎悠也,西野浩輔,光田直人,井川和宣, 友岡克彦
    • Organizer
      第31回有機合成化学セミナー
    • Place of Presentation
      福岡
    • Year and Date
      2014-09-17 – 2014-09-19
    • Related Report
      2014 Annual Research Report
  • [Presentation] Addition-Type Ozone Oxidation of Silylalkenes and Its Synthetic Applications2014

    • Author(s)
      K. Igawa
    • Organizer
      The 17th International Symposium on Silicon Chemistry
    • Place of Presentation
      Berlin, Germany
    • Year and Date
      2014-08-03 – 2014-08-08
    • Related Report
      2014 Annual Research Report
  • [Presentation] 新規キラル分子の創出 : キラルケイ素分子の不斉合成2013

    • Author(s)
      井川和宣
    • Organizer
      日本薬学会第133年会
    • Place of Presentation
      パシフィコ横浜
    • Year and Date
      2013-03-28
    • Related Report
      2012 Annual Research Report
  • [Presentation] シリル置換不飽和結合の特異な反応性を活用した効率的分子変換法の開発2013

    • Author(s)
      井川和宣
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学BKC
    • Year and Date
      2013-03-23
    • Related Report
      2012 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成とその変換(1)2013

    • Author(s)
      井川和宣, 吉廣大佑, 市川延雅, 友岡克彦
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学BKC
    • Year and Date
      2013-03-22
    • Related Report
      2012 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成とその変換(2)2013

    • Author(s)
      井川和宣, 吉廣大佑, 市川延雅, 古閑直人, 友岡克彦
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      立命館大学BKC
    • Year and Date
      2013-03-22
    • Related Report
      2012 Annual Research Report
  • [Presentation] Significant Silyl Substituent Effect on Ozone Oxidation : A Novel Approach to Multi-oxy-functionalized Compounds from Alkynes2012

    • Author(s)
      K. Igawa, Y. Kawasaki, M. Murakami, K. Sakita, Y. Ishikawa, K. Tomooka
    • Organizer
      The 4th Asian Silicon Symposium
    • Place of Presentation
      立命館大学BKC
    • Year and Date
      2012-10-23
    • Related Report
      2012 Annual Research Report
  • [Presentation] シラシクロペンテンオキシドのエナンチオ選択的β-脱離反応

    • Author(s)
      吉廣大佑,安部雄介,井川和宣,友岡克彦
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学,名古屋
    • Related Report
      2013 Annual Research Report
  • [Presentation] キラル有機ケイ素分子の不斉合成

    • Author(s)
      井川和宣
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学,名古屋
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] キラルケイ素分子の不斉合成:その反応設計と実践

    • Author(s)
      井川和宣
    • Organizer
      熊本大学自然科学研究科第1回キラル分子科学研究会
    • Place of Presentation
      熊本大学,熊本
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Asymmetric Ozone Oxidation of Alkene Having Chiral Silyl Group

    • Author(s)
      Kazunobu Igawa, Yuuya Kawasaki, Kosuke Nishino, Naoto Mitsuda, Katsuhiko Tomooka
    • Organizer
      The 3rd International Conference on the MEXT Project of Integrated Research on Chemical Synthesis
    • Place of Presentation
      Kyushu Univ., Fukuoka, Japan
    • Related Report
      2013 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Alkenylhydrosilane and Its Stereoselective Transformation

    • Author(s)
      Kazunobu Igawa, Daisuke Yoshihiro, Nobumasa Ichikawa, Naoto Kokan, Katsuhiko Tomooka
    • Organizer
      The 3rd International Conference on the MEXT Project of Integrated Research on Chemical Synthesis
    • Place of Presentation
      Kyushu Univ., Fukuoka, Japan
    • Related Report
      2013 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Alkenylhydrosilane and Its Stereoselective Transformation

    • Author(s)
      Kazunobu Igawa, Daisuke Yoshihiro, Nobumasa Ichikawa, Naoto Kokan, Katsuhiko Tomooka
    • Organizer
      The Eighth International Symposium on Integrated Synthesis
    • Place of Presentation
      Nara, Japan
    • Related Report
      2013 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成とその変換

    • Author(s)
      吉廣大佑,市川延雅,古閑直人,井川和宣,友岡克彦
    • Organizer
      第4回統合物質シンポジウム
    • Place of Presentation
      北海道大学,札幌
    • Related Report
      2013 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成:キラル白金触媒を用いたエナンチオ選択的ヒドロシリル化反応の開発

    • Author(s)
      井川和宣,吉廣大佑,市川延雅,古閑直人,友岡克彦
    • Organizer
      第17回ケイ素化学協会シンポジウム
    • Place of Presentation
      箱根湯本温泉ホテルおかだ,箱根湯本
    • Related Report
      2013 Annual Research Report
  • [Presentation] 新規キラルヒドロシランTADDOSi-Hを活用した不斉オゾン酸化反応の開発

    • Author(s)
      井川和宣,光田直人,河崎悠也,西野浩輔,友岡克彦
    • Organizer
      第17回ケイ素化学協会シンポジウム
    • Place of Presentation
      箱根湯本温泉ホテルおかだ,箱根湯本
    • Related Report
      2013 Annual Research Report
  • [Presentation] ケイ素の特性を活用した効率的分子変換法の開発と新分子の創出

    • Author(s)
      井川和宣
    • Organizer
      第30回有機合成化学セミナー
    • Place of Presentation
      せとうち児島ホテル,倉敷
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] ジヒドロシランの不斉非対称化を伴うヒドロシリル化反応:アルケニルヒドロシランの触媒的不斉合成法の開発

    • Author(s)
      吉廣大佑,市川延雅,古閑直人,井川和宣,友岡克彦
    • Organizer
      有機合成化学協会九州山口支部第25回若手研究者のためのセミナー
    • Place of Presentation
      九州大学,福岡
    • Related Report
      2013 Annual Research Report
  • [Presentation] 不斉オゾン酸化反応を活用した光学活性アシロイン類の合成

    • Author(s)
      井川和宣,光田直人,西野浩輔,河崎悠也,友岡克彦
    • Organizer
      有機合成化学協会九州山口支部第25回若手研究者のためのセミナー
    • Place of Presentation
      九州大学,福岡
    • Related Report
      2013 Annual Research Report
  • [Presentation] Reaction Control Using Silyl-substituent Effects: Synthesis of Silylalkenes and Their Ozone Oxidation

    • Author(s)
      Kazunobu Igawa
    • Organizer
      The First Asian Conference for "MONODUKURI" Strategy by Synthetic Organic Chemistry
    • Place of Presentation
      Okinawa, Japan
    • Related Report
      2013 Annual Research Report
    • Invited
  • [Presentation] Enantioselective Synthesis of Alkenylhydrosilane: Desymmetric Hydrosilylation of Dihydrosilane

    • Author(s)
      Kazunobu Igawa, Kouhei Machida, Kazuhiro Uehara, Katsuhiko Tomooka
    • Organizer
      The First Asian Conference for "MONODUKURI" Strategy by Synthetic Organic Chemistry
    • Place of Presentation
      Okinawa, Japan
    • Related Report
      2013 Annual Research Report
  • [Presentation] アルケニルヒドロシランの触媒的不斉合成

    • Author(s)
      井川和宣,吉廣大佑,市川延雅,古閑直人,友岡克彦
    • Organizer
      第103回有機合成シンポジウム
    • Place of Presentation
      慶応義塾大学,東京
    • Related Report
      2013 Annual Research Report
  • [Presentation] キラルケイ素分子の不斉合成:アルケニルヒドロシランの触媒的不斉合成とその変換

    • Author(s)
      井川和宣,吉廣大佑,市川延雅,古閑直人,友岡克彦
    • Organizer
      第23回万有福岡シンポジウム
    • Place of Presentation
      九州大学,福岡
    • Related Report
      2013 Annual Research Report
  • [Book] Silanecarboxylic Acids and Esters in Science of Synthesis2013

    • Author(s)
      K. Igawa, K. Tomooka (Eds; D. G. Hall, M. North, M. Oestreich)
    • Total Pages
      6
    • Publisher
      Thieme
    • Related Report
      2013 Annual Research Report

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Published: 2012-04-24   Modified: 2019-07-29  

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