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Development of Catalytic Methods for Construction of Stereogenic Centers through Bond Formation with Sterically Demanding sp3 Carbons

Research Project

Project/Area Number 26288048
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

Ohmura Toshimichi  京都大学, 工学(系)研究科(研究院), 准教授 (00378803)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥16,900,000 (Direct Cost: ¥13,000,000、Indirect Cost: ¥3,900,000)
Fiscal Year 2016: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2015: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2014: ¥8,840,000 (Direct Cost: ¥6,800,000、Indirect Cost: ¥2,040,000)
Keywords不斉化学合成 / 合成化学 / 有機ホウ素化合物 / 遷移金属触媒 / 触媒的分子変換
Outline of Final Research Achievements

The principle investigator established an efficient iridium catalyst system for conversion of sterically demanding C(sp3)-H bonds into C(sp3)-B bonds. He also found an iridium-catalyzed addition of C(sp3)-H bond across carbon-carbon multiple bonds, namely hydroalkylation. New insights into α-aminoalkylboron reagents in stereospecific Suzuki-Miyaura coupling, as well as in nucleophilic carbon-carbon bond formation mediated by alkali metal alkoxides, is obtained in the present study. These findings are valuable for rapid production of enantioenriched chiral molecules, which would innovate drug and functional material developments and researches involving chiral recognition.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • Research Products

    (46 results)

All 2017 2016 2015 2014 Other

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (42 results) (of which Int'l Joint Research: 15 results,  Invited: 6 results) Remarks (1 results)

  • [Journal Article] Utilization of a Trimethylsilyl Group as a Synthetic Equivalent of a Hydroxyl Group via Chemoselective C(sp3)-H Borylation at the Methyl Group on Silicon2017

    • Author(s)
      Takeru Torigoe, Toshimichi Ohmura, Michinori Suginome
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 82 Issue: 6 Pages: 2943-2956

    • DOI

      10.1021/acs.joc.6b02917

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A (Borylmethyl)silane Bearing Three Hydrolyzable Groups on Silicon: Synthesis via Iridium-Catalyzed C(sp3)-H Borylation and Conversion to Functionalized Siloxanes2016

    • Author(s)
      Ohmura, T.; Sasaki, I.; Torigoe, T.; Suginome, M.
    • Journal Title

      Organometallics

      Volume: 35 Issue: 11 Pages: 1601-1603

    • DOI

      10.1021/acs.organomet.6b00316

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Intramolecular Methoxy C-H Addition to Carbon-Carbon Triple Bond: Direct Synthesis of 3-Substituted Benzofurans from o Methoxyphenylalkynes2016

    • Author(s)
      Torigoe, T.; Ohmura, T.; Suginome, M.
    • Journal Title

      Chem. Eur. J.

      Volume: 22 Issue: 30 Pages: 10415-10419

    • DOI

      10.1002/chem.201602152

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Presentation] Synthesis of Organometallic Compounds and Heterocycles Based on Iridium-Catalyzed C(sp3)-H Bond Activation2017

    • Author(s)
      Toshimichi Ohmura, Ikuo Sassaki, Michinori Suginome
    • Organizer
      The 13th Kinki-Youngnam Joint Symposium on Organometallic Chemistry
    • Place of Presentation
      Kyoto, Japan
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Nickel-Catalyzed Alkene-Alkene-Silylene [2+2+1] Cycloaddition with Use of (Aminosilyl)boronic Esters as a Synthetic Equivalent of Silylene2017

    • Author(s)
      Toshimichi Ohmura, Ikuo Sasaki, Michinori Suginome
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス、横浜
    • Related Report
      2016 Annual Research Report
  • [Presentation] α-アミノアルキルホウ素反応剤を用いる有機ハロゲン化物の無触媒α-アミノアルキル化2017

    • Author(s)
      大村 智通、杉原 弘亮、杉野目 道紀
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス、横浜
    • Related Report
      2016 Annual Research Report
  • [Presentation] Iridium-Catalyzed Enantioselective Intramolecular Addition of N-Methyl C-H Bond across C-C Double Bond Giving Dihydroindoles2017

    • Author(s)
      Takeru Torigoe, Toshimichi Ohmura, Michinori Suginome
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス、横浜
    • Related Report
      2016 Annual Research Report
  • [Presentation] イリジウム触媒による炭素-炭素二重結合へのメトキシC-H結合の分子内付加反応2017

    • Author(s)
      大村智通、日下智史、鳥越尊、杉野目道紀
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応義塾大学日吉キャンパス、横浜
    • Related Report
      2016 Annual Research Report
  • [Presentation] イリジウム触媒によるシロキサン化合物のマルチC(sp3)-Hホウ素化2016

    • Author(s)
      大村智通、恵村一木、鳥越尊、杉野目 道紀
    • Organizer
      日本化学会 第96春季年会
    • Place of Presentation
      同志社大学、京田辺
    • Year and Date
      2016-03-25
    • Related Report
      2015 Annual Research Report
  • [Presentation] Iridium-Catalyzed Intramolecular Addition of C(sp3)-H Bond to Carbon-Carbon Triple Bond2016

    • Author(s)
      Takeru Torigoe, Toshimichi Ohmura, Michinori Suginome
    • Organizer
      日本化学会 第96春季年会
    • Place of Presentation
      同志社大学、京田辺
    • Year and Date
      2016-03-25
    • Related Report
      2015 Annual Research Report
  • [Presentation] (アミノシリル)ボランを用いた無触媒シリレン挿入を鍵とする アルコキシシランのアルコキシジシランへの変換2016

    • Author(s)
      大村智通、佐々木郁雄、杉野目道紀
    • Organizer
      日本化学会 第96春季年会
    • Place of Presentation
      同志社大学、京田辺
    • Year and Date
      2016-03-25
    • Related Report
      2015 Annual Research Report
  • [Presentation] イリジウム触媒によるsp3炭素-水素結合ホウ素化に基づく官能性ポリシロキサン合成2016

    • Author(s)
      大村智通、佐々木郁雄、鳥越尊、杉野目道紀
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザ神戸、神戸
    • Related Report
      2016 Annual Research Report
  • [Presentation] Use of Amino(beryl)silane as a Synthetic Equivalent of Silylene under Transition-Metal-Free Conditions2016

    • Author(s)
      Toshimichi Ohmura, Ikuo Sasaki, Michinori Suginome
    • Organizer
      47th Silicon Symposium
    • Place of Presentation
      Oregon, America
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Iridium-Catalyzed Intramolecular Hydroalkylation of Alkynes via C(sp3)-H Activation at a Methoxy Group2016

    • Author(s)
      Takeru Torigoe, Toshimichi Ohmura, Michinori Suginome
    • Organizer
      17th Tetrahedron Symposium
    • Place of Presentation
      Sitges, Spain
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Multiple Functionalization of Dimethylpolysiloxanes Based on Iridium-Catalyzed C(sp3)-H Borylation2016

    • Author(s)
      Toshimichi Ohmura, Kazuki Emura, Takeru Torigoe, Michinori Suginome
    • Organizer
      20th International Symposium on Homogeneous Catalysis (ISHCXX)
    • Place of Presentation
      Kyoto, Japan
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 4,4'-Bipyridine-Catalyzed Diboration of Pyrazines: B-B Bond Activation through Radical Pathway2016

    • Author(s)
      Toshimichi Ohmura, Yohei Morimasa, Michinori Suginome, Yasujiro Murata, Tomoya Ichino, Tetsuya Taketsugu, Satoshi Maeda
    • Organizer
      20th International Symposium on Homogeneous Catalysis (ISHCXX)
    • Place of Presentation
      Kyoto, Japan
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Multiple C(sp3)-H Borylation Using Ir/t-BuOK Catalyst System for the Synthesis of Functionalized Dimethylpolysiloxanes2016

    • Author(s)
      Toshimichi Ohmura, Kazuki Emura, Takeru Torigoe, Michinori Suginome
    • Organizer
      he 3rd International Conference on Organometallics and Catalysis (OM&Cat 2016)
    • Place of Presentation
      Seoul, Korea
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] メトキシC-H結合のアセチレンへのイリジウム触媒分子内ヒドロアルキル化に基づくベンゾフラン合成2016

    • Author(s)
      鳥越尊、大村智通、杉野目道紀
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学、東京
    • Related Report
      2016 Annual Research Report
  • [Presentation] 3つの加水分解性基を有するメチルシランの化学選択的C(sp3)-Hボリル化に基づく官能性ポリシロキサン合成2016

    • Author(s)
      大村智通、佐々木郁雄、鳥越尊、杉野目道紀
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学、東京
    • Related Report
      2016 Annual Research Report
  • [Presentation] イリジウム触媒多重C(sp3)-Hホウ素化に基づくジメチルポリシロキサンの官能基化2016

    • Author(s)
      大村智通、恵村一木、鳥越尊、杉野目道紀
    • Organizer
      第20回ケイ素化学協会シンポジウム
    • Place of Presentation
      安芸グランドホテル、広島
    • Related Report
      2016 Annual Research Report
  • [Presentation] Iridium-Catalyzed Sequential Activation of C(sp3)-H Bonds: Benzofuran Synthesis through Intramolecular Hydroalkylation Followed by Double Bond Migration2016

    • Author(s)
      Toshimichi Ohmura, Takeru Torigoe, Michinori Suginome
    • Organizer
      ACP-2016-Koria
    • Place of Presentation
      Daejeon, Korea
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Iridium-Catalyzed Chemoselective C(sp3)-H Functionalization for Synthesis of Organoboron Compounds and Heterocycles2016

    • Author(s)
      Toshimichi Ohmura
    • Organizer
      Catalysis and Fine Chemicals 2016 (C&FC 2016)
    • Place of Presentation
      Taipei, Taiwan
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] α-(Acylamino)benzylboronic Esters as a Synthon of α-Aminobenzyl Anion for Synthesis of Nitrogen-Containing Organic Compounds2016

    • Author(s)
      Toshimichi Ohmura, Kousuke Sugihara, Michinori Suginome
    • Organizer
      21st International Conference on Organic Synthesis
    • Place of Presentation
      Mumbai, India
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Novel Molecular Transformations Based on Catalytic Activation of Boron-Containing σ-Bonds by Transition Metals or 4,4’-Bipyridines2015

    • Author(s)
      Toshimichi Ohmura
    • Organizer
      Pacifichem 2015
    • Place of Presentation
      Honolulu, Hawaii, USA
    • Year and Date
      2015-12-18
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ホウ素反応剤を用いる触媒的分子変換反応の開拓 -常識を越える新反応を求めて-2015

    • Author(s)
      大村智通
    • Organizer
      触媒学会有機金属研究会  オルガノメタリックセミナー2015 「新しい分子変換に挑戦する有機金属化学」
    • Place of Presentation
      東北大学
    • Year and Date
      2015-10-30
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] トリアルコキシメチルシランのケイ素上メチル基選択的CーHホウ素化2015

    • Author(s)
      大村智通、佐々木郁雄、鳥越尊、杉野目道紀
    • 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] イリジウム触媒炭素-水素結合ホウ素化を鍵とするジメチルシラシクロペンタン の 1,4-ジオールへの変換2015

    • Author(s)
      鳥越尊、大村智通、杉野目道紀
    • 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] シレン合成等価体として利用可能なボリルシランの開発2015

    • Author(s)
      大村智通、西浦弘樹、杉野目道紀
    • 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] Catalytic C(sp3)-H Borylation-Based Functionalization of Methylalkoxysilanes2015

    • Author(s)
      Toshimichi Ohmura, Ikuo Sasaki, Takeru Torigoe, Michinori Suginome
    • Organizer
      The 5th Asian Silicon Symposium jointly with the 3rd International Symposium on Applied Silicon Chemistry (ASIS-5, ISASC-3)
    • Place of Presentation
      Jeju, Korea
    • Year and Date
      2015-10-19
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] An (Aminomethyl)borylsilane as a Synthetic Equivalent of Silene under Palladium-Catalyzed Conditions2015

    • Author(s)
      Toshimichi Ohmura, Hiroki Nishiura, Michinori Suginome
    • Organizer
      The 5th Asian Silicon Symposium jointly with the 3rd International Symposium on Applied Silicon Chemistry (ASIS-5, ISASC-3)
    • Place of Presentation
      Jeju, Korea
    • Year and Date
      2015-10-19
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of Chiral Amines via Catalytic Carbon-Carbon Bond Formation Using Enantioenriched α-(Acetylamino)alkylboron Compounds2015

    • Author(s)
      Toshimichi Ohmura, Kyoko Miwa, Kousuke Sugihara, Michinori Suginome
    • Organizer
      IUPAC-2015 45th World Chemistry Congress
    • Place of Presentation
      Busan, South Korea
    • Year and Date
      2015-08-10
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Novel Molecular Transformations Using Boron Reagents and Catalysts2015

    • Author(s)
      Toshimichi Ohmura
    • Organizer
      Chuo Organometallic Seminar
    • Place of Presentation
      Chuo University, Tokyo
    • Year and Date
      2015-06-27
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Enabling Oxidative Conversion of Alkyltrimethylsilanes to Alkanols by Chemoselective C-H Borylation at Methyl Group on Silicon2015

    • Author(s)
      Toshimichi Ohmura, Takeru Torigoe, Michinori Suginome
    • Organizer
      46th Silicon Symposium
    • Place of Presentation
      University of California, Davis campus, USA
    • Year and Date
      2015-06-22
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] (アミノメチル)シリルボラン:パラジウム触媒を用いるシレン合成等価体としての利用2015

    • Author(s)
      大村智通、西浦弘樹、杉野目道紀
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] イリジウム触媒によるメチルアルコキシシランのケイ素上メチル基選択的sp3炭素-水素結合ホウ素化2015

    • Author(s)
      大村智通、佐々木郁雄、鳥越尊、杉野目道紀
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2015-03-27
    • Related Report
      2014 Annual Research Report
  • [Presentation] Highly-Efficient Ir/t-BuOK Catalyst for Non-Directed C(sp3)-H Borylation2015

    • Author(s)
      Toshimichi Ohmura, Takeru Torigoe, Michinori Suginome
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2015-03-27
    • Related Report
      2014 Annual Research Report
  • [Presentation] ホウ素反応剤を用いる触媒的分子変換の新展開2015

    • Author(s)
      大村智通
    • Organizer
      近畿化学協会ヘテロ原子部会平成26年度第3回懇話会
    • Place of Presentation
      大阪科学技術センター
    • Year and Date
      2015-02-12
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] C(sp3)-H Bond Activation without Assistance of Coordinating Functional Groups: Iridium-Catalyzed C-H Borylation of Alkylsilanes and Aliphatic Compounds2014

    • Author(s)
      Toshimichi Ohmura, Takeru Torigoe, Michinori Suginome
    • Organizer
      The 2nd International Conference on Organometallics and Catalysis (OM&Cat-2014)
    • Place of Presentation
      東大寺総合文化センター(奈良県)
    • Year and Date
      2014-10-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] 触媒的炭素-水素結合ホウ素化を鍵とするトリメチルシリル基の水酸基への変換2014

    • Author(s)
      大村智通、鳥越尊、杉野目道紀
    • Organizer
      第18回ケイ素化学協会シンポジウム
    • Place of Presentation
      ラフォーレ那須(栃木県)
    • Year and Date
      2014-10-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] 非ベンジル型α-(アシルアミノ)アルキルホウ素反応剤の立体特異的鈴木-宮浦カップリング2014

    • Author(s)
      大村智通、三輪恭子、杉野目道紀
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学
    • Year and Date
      2014-09-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] イリジウム触媒よる立体的に混み合ったsp3炭素-水素結合の高効率ボリル化2014

    • Author(s)
      大村智通、鳥越尊、杉野目道紀
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学
    • Year and Date
      2014-09-24
    • Related Report
      2014 Annual Research Report
  • [Presentation] Catalytic Construction of Stereogenic Carbon Centers via Stereospecific Suzuki-Miyaura Coupling of α-(Acylamino)alkylboron Reagents2014

    • Author(s)
      Toshimichi Ohmura, Kyoko Miwa, Michinori Suginome
    • Organizer
      The 26th International Conference on Organometallic Chemistry (ICOMC-26)
    • Place of Presentation
      ロイトン札幌
    • Year and Date
      2014-07-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] Catalytic Functionalization of Sterically Hindered C(sp3)-H Bonds: An Efficient Iridium Catalyst System for Directing Group-Free C-H Borylation2014

    • Author(s)
      Toshimichi Ohmura, Takeru Torigoe, Michinori Suginome
    • Organizer
      The 19th International Symposium on Homogeneous Catalysis (ISHC-19)
    • Place of Presentation
      Ottawa Convention Center, Canada
    • Year and Date
      2014-07-10
    • Related Report
      2014 Annual Research Report
  • [Presentation] Functionalization of Organosilicon Feedstocks and Their Derivatives via Catalytic Borylation of the C(sp3)-H Bonds2014

    • Author(s)
      Toshimichi Ohmura
    • Organizer
      2014 Canada-Japan Workshop
    • Place of Presentation
      Ottawa University, Canada
    • Year and Date
      2014-07-04
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] 配位性官能基に依存しないsp3炭素-水素結合活性化:イリジウム触媒によるアルキルシランおよび脂肪族化合物のC-Hホウ素化2014

    • Author(s)
      大村智通
    • Organizer
      新学術領域研究「分子活性化」第7回公開シンポジウム
    • Place of Presentation
      北海道大学
    • Year and Date
      2014-06-20
    • Related Report
      2014 Annual Research Report
  • [Remarks] 研究室ホームページ

    • URL

      http://www.sbchem.kyoto-u.ac.jp/suginome-lab/jp/

    • Related Report
      2016 Annual Research Report 2015 Annual Research Report 2014 Annual Research Report

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Published: 2014-04-04   Modified: 2018-03-22  

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