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Development of Catalytic Carboxylation of C(sp3)-H Bonds with Carbon Dioxide

Research Project

Project/Area Number 26410108
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionHokkaido University

Principal Investigator

MITA Tsuyoshi  北海道大学, 薬学研究院, 助教 (00548183)

Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥4,000,000、Indirect Cost: ¥1,200,000)
Fiscal Year 2016: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2015: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2014: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords二酸化炭素 / C-H結合活性化 / カルボキシル化 / C(sp3)-H結合 / 遷移金属錯体 / コバルト / トリメチルアルミニウム / ラクトン / C-H活性化 / ロジウム / メタラサイクル
Outline of Final Research Achievements

A catalytic carboxylation of the allylic C(sp3)-H bond of terminal alkenes with CO2 was developed with the aid of a cobalt/Xantphos complex. A wide range of allylarenes and 1,4-dienes were successfully transformed into the linear styrylacetic acid and hexa-3,5-dienoic acid derivatives in moderate to high yields, with excellent regioselectivity. The carboxylation showed remarkable functional group tolerability, so that selective addition to CO2 occurred in the presence of other carbonyl groups such as amide, ester, and ketone. Since styrylacetic acid derivatives can be readily converted into optically active γ-butyrolactones through Sharpless asymmetric dihydroxylation, this allylic C(sp3)-H carboxylation showcases a facile synthesis of γ-butyrolactones from simple allylarenes via short steps.

Report

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

    (40 results)

All 2017 2016 2015 2014 Other

All Journal Article (11 results) (of which Peer Reviewed: 11 results,  Acknowledgement Compliant: 7 results,  Open Access: 1 results) Presentation (25 results) (of which Int'l Joint Research: 6 results,  Invited: 3 results) Book (2 results) Remarks (2 results)

  • [Journal Article] Cobalt-Catalyzed Allylic C(sp3)-H Carboxylation with CO22017

    • Author(s)
      Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 17 Pages: 6094-6097

    • DOI

      10.1021/jacs.7b02775

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Stereoretentive Addition of N-tert-Butylsulfonyl-α-Amido Silanes to Aldehydes, Ketones, α,β-Unsaturated Esters, and Imines2016

    • Author(s)
      Tsuyoshi Mita, Keisuke Saito, Masumi Sugawara, Yoshihiro Sato
    • Journal Title

      Chemistry An Asian Journal

      Volume: 11 Issue: 10 Pages: 1528-1531

    • DOI

      10.1002/asia.201600270

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Palladium-Catalyzed Carboxylation of Activated Vinylcyclopropanes with CO22016

    • Author(s)
      Tsuyoshi Mita, Yuki Higuchi, and Yoshihiro Sato
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 11 Pages: 2754-2757

    • DOI

      10.1021/acs.orglett.6b01231

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Synthesis of α-Amino Acids through Carboxylation of Ammonium Ylides with CO2 Followed by Alkyl Migration2016

    • Author(s)
      Tsuyoshi Mita, Masumi Sugawara, Yoshihiro Sato
    • Journal Title

      Journal of Organic Chemistry

      Volume: 81 Issue: 12 Pages: 5236-5243

    • DOI

      10.1021/acs.joc.6b00837

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions2015

    • Author(s)
      Tsuyoshi Mita, Kenta Suga, Kaori Sato, Yoshihiro Sato
    • Journal Title

      Organic Letters

      Volume: 17 Issue: 21 Pages: 5276-5279

    • DOI

      10.1021/acs.orglett.5b02645

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Highly Regioselective Palladium-Catalyzed Carboxylation of Allylic Alcohols with CO22015

    • Author(s)
      Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    • Journal Title

      Chemistry - A European Journal

      Volume: 21 Issue: 46 Pages: 16391-16394

    • DOI

      10.1002/chem.201503359

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] C(sp3)-H結合のシリル化およびトリホウ素化、続く二酸化炭素によるカルボキシル化の開発2015

    • Author(s)
      美多 剛
    • Journal Title

      有機合成化学協会誌

      Volume: 73 Pages: 810-820

    • NAID

      130005098864

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Carboxylation with CO_2 via Brook Rearrangement : Preparation of α-Hydroxy Acid Derivatives2014

    • Author(s)
      Tsuyoshi Mita, Yuki Higuchi, and Yoshihiro Sato
    • Journal Title

      Org. Lett

      Volume: 16 Issue: 1 Pages: 14-17

    • DOI

      10.1021/ol403099f

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Arylglycines from CO_2 through α-Amino Organomanganese Species2014

    • Author(s)
      Tsuyoshi Mita, Jianyang Chen, and Yoshihiro Sato
    • Journal Title

      Org. Lett

      Volume: 16 Issue: 8 Pages: 2200-2203

    • DOI

      10.1021/ol500701n

    • Related Report
      2014 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ru-Catalyzed C-H Silylation of 1-Arylpyrazole Derivatives and Fluoride-Mediated Carboxylation: Use of Two Nitrogen Atomes of the Pyrazole Group2014

    • Author(s)
      Tsuyoshi Mita, Hiroyuki Tanaka, Kenichi Michigami, Yoshihiro Sato
    • Journal Title

      Synlett

      Volume: 25 Issue: 09 Pages: 1291-1294

    • DOI

      10.1055/s-0033-1341230

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Catalytic Enantioselective Silylation of N-Sulfonylimines: Asymmetric Synthesis of α-Amino Acids from CO2 via Stereospecific Carboxylation of α-Amino Silanes2014

    • Author(s)
      Tsuyoshi Mita, Masumi Sugawara, Keisuke Saito, and Yoshihiro Sato
    • Journal Title

      Organic Letters

      Volume: 16 Issue: 11 Pages: 3028-3031

    • DOI

      10.1021/ol501143c

    • Related Report
      2014 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 二酸化炭素を用いたコバルト触媒によるアリル位C(sp3)-H結合カルボキシル化反応の開発2017

    • Author(s)
      道上 健一、美多 剛、佐藤 美洋
    • Organizer
      日本薬学会第137年会
    • Place of Presentation
      東北大学川内北キャンパス(宮城県仙台市)
    • Year and Date
      2017-03-24
    • Related Report
      2016 Annual Research Report
  • [Presentation] アリル位C(sp3)-H結合活性化を伴うケトン類の触媒的アリル化反応の開発2017

    • Author(s)
      花形 聡、道上 健一、美多 剛、佐藤 美洋
    • Organizer
      日本薬学会第137年会
    • Place of Presentation
      東北大学川内北キャンパス(宮城県仙台市)
    • Year and Date
      2017-03-24
    • Related Report
      2016 Annual Research Report
  • [Presentation] 二酸化炭素を用いたパラジウム触媒によるインドリルメタノール誘導体のカルボキシル化反応2017

    • Author(s)
      石井 聖、樋口 裕紀、美多 剛、佐藤 美洋
    • Organizer
      日本薬学会第137年会
    • Place of Presentation
      東北大学川内北キャンパス(宮城県仙台市)
    • Year and Date
      2017-03-24
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis of α-Amino Acids from Carbon Dioxide2016

    • Author(s)
      Tsuyoshi Mita
    • Organizer
      HU-SNU Joint Symposium
    • Place of Presentation
      北海道大学薬学部、臨床薬学講義室(北海道札幌市)
    • Year and Date
      2016-11-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cobalt-Catalyzed Carboxylation of Allylic C-H Bond with Carbon Dioxide2016

    • Author(s)
      Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      The 11th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      大田広域市(大韓民国)
    • Year and Date
      2016-10-27
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cobalt-Catalyzed Carboxylation of Allylic C-H Bond with Carbon Dioxide2016

    • Author(s)
      Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      The 6st Junior International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      九州大学筑紫キャンパスC-CUBE(福岡県福岡市)
    • Year and Date
      2016-10-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 求核性アリルパラジウム種を利用した新規二酸化炭素固定化反応の開発2016

    • Author(s)
      樋口 裕紀、美多 剛、佐藤 美洋
    • Organizer
      第46回複素環化学討論会
    • Place of Presentation
      金沢歌劇座(石川県金沢市)
    • Year and Date
      2016-09-26
    • Related Report
      2016 Annual Research Report
  • [Presentation] コバルト触媒と二酸化炭素によるアリル位C-H結合カルボキシル化反応の開発2016

    • Author(s)
      道上 健一、美多 剛、佐藤 美洋
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス(東京都新宿区)
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] コバルト触媒と二酸化炭素によるアリル位 C(sp3)-H 結合カルボキシル化反応の開発2016

    • Author(s)
      道上 健一、美多 剛、佐藤 美洋
    • Organizer
      万有プレシンポジウム
    • Place of Presentation
      北海道大学薬学部、第一講義室(北海道札幌市)
    • Year and Date
      2016-07-01
    • Related Report
      2016 Annual Research Report
  • [Presentation] Copper-Catalyzed Enantioselective Silylation Followed by Stereoretentive Addition to Carbon Electrophiles2016

    • Author(s)
      Tsuyoshi Mita, Masumi Sugawara, Keisuke Saito, Yoshihiro Sato
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      ナレッジキャピタルコングレコンベンションセンター(大阪府大阪市)
    • Year and Date
      2016-04-20
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 二酸化炭素を一炭素源とした環状ジシランによる有機ハロゲン化合物のカルボキシル化反応の開発2016

    • Author(s)
      菅 健太、美多 剛、佐藤 香、佐藤 美洋
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜(神奈川県横浜市)
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
  • [Presentation] 二酸化炭素を利用した Pd 触媒によるアリルアルコールのカルボキシル化反応の開発2016

    • Author(s)
      樋口 裕紀、美多 剛、佐藤 美洋
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜(神奈川県横浜市)
    • Year and Date
      2016-03-26
    • Related Report
      2015 Research-status Report
  • [Presentation] 二酸化炭素を用いたα-アミノ酸の化学合成2015

    • Author(s)
      美多 剛
    • Organizer
      第10回プロセス化学ラウンジ
    • Place of Presentation
      和光純薬工業㈱湯河原研修所(静岡県熱海市)
    • Year and Date
      2015-12-04
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] アンモニウムイリドのカルボキシル化を経由するCO2を用いたα-アミノ酸のワンポット合成2015

    • Author(s)
      菅原 真純、美多 剛、佐藤 美洋
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      早稲田大学国際会議場(東京都新宿区)
    • Year and Date
      2015-11-19
    • Related Report
      2015 Research-status Report
  • [Presentation] 二酸化炭素を一炭素源として用いた新規カルボキシル化反応の開発2015

    • Author(s)
      美多 剛
    • Organizer
      第32回有機合成化学セミナー
    • Place of Presentation
      ニューウェルシティー湯河原(静岡県熱海市)
    • Year and Date
      2015-09-15
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] 二酸化炭素を一炭素源とした環状ジシランによるアリール、アルケニル及びアルキニルハライドのカルボキシル化反応の開発2015

    • Author(s)
      菅 健太、美多 剛、佐藤 香、佐藤 美洋
    • Organizer
      第27回札幌万有シンポジウム
    • Place of Presentation
      北海道大学工学部オープンホール(北海道札幌市)
    • Year and Date
      2015-07-04
    • Related Report
      2015 Research-status Report
  • [Presentation] Carboxylation of Halocarbons with CO2 Using a Structurally Strained Disilane2015

    • Author(s)
      Kenta Suga, Tsuyoshi Mita, Kaori Sato, Yoshihiro Sato
    • Organizer
      OMCOS18
    • Place of Presentation
      Hotel Melia Sitges(スペイン)
    • Year and Date
      2015-06-28
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] One-Pot Synthesis of α-Amino Acids from CO2 and Imine Equivalents2015

    • Author(s)
      Tsuyoshi Mita, Masumi Sugawara, Jianyang Chen, Yuki Higuchi, Yoshihiro Sato
    • Organizer
      Organic Chemistry Symposium, Royal Society of Chemistry Roadshow
    • Place of Presentation
      青葉サイエンスホール、東北大学(宮城県仙台市)
    • Year and Date
      2015-06-01
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] イリジウム触媒によるエナンチオ選択的C-Hホウ素化反応の開発2015

    • Author(s)
      美多 剛、池田 祐人、佐藤 美洋
    • Organizer
      日本薬学会第135年会
    • Place of Presentation
      デザイン・クリエイティブセンター神戸(神戸)
    • Year and Date
      2015-03-26 – 2015-03-28
    • Related Report
      2014 Research-status Report
  • [Presentation] Asymmetric Synthesis of α-Amino Acids Using CO2 via Copper-Catalyzed Silylation Followed by Stereospecific Carboxylation2014

    • Author(s)
      Tsuyoshi Mita, Masumi Sugawara, Keisuke Saito, Yoshihiro Sato
    • Organizer
      The 9th International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      Eastin Hotel Petaling Jaya (Selangor, Malaysia)
    • Year and Date
      2014-12-01 – 2014-12-05
    • Related Report
      2014 Research-status Report
  • [Presentation] One-Pot Synthesis of α-Amino Acids and α-Hydroxy Acids from Aldehydes and Carbon Dioxide2014

    • Author(s)
      Yuki Higuchi, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      26th International Conference on Organometallic Chemistry (ICOMC-2014)
    • Place of Presentation
      Royton Sapporo (Sapporo, Japan)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Iridium(I)- and Rhodium(I)-Catalyzed Intermolecular Dehydrogenative Silylation of C(sp3)-H Bonds Adjacent to a Nitrogen Atom2014

    • Author(s)
      Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      26th International Conference on Organometallic Chemistry (ICOMC-2014)
    • Place of Presentation
      Royton Sapporo (Sapporo, Japan)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Synthesis of Triborylated Compounds via Iridium-Catalyzed Triple Activation of Primary C(sp3)-H Bonds2014

    • Author(s)
      Yuto Ikeda, Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      26th International Conference on Organometallic Chemistry (ICOMC-2014)
    • Place of Presentation
      Royton Sapporo (Sapporo, Japan)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] Ruthenium-Catalyzed C(sp2)-H Silylation of Arylpyrazoles Followed by Carboxylation with CO22014

    • Author(s)
      Hiroyuki Tanaka, Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    • Organizer
      26th International Conference on Organometallic Chemistry (ICOMC-2014)
    • Place of Presentation
      Royton Sapporo (Sapporo, Japan)
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Research-status Report
  • [Presentation] 芳香族C-H結合の触媒的シリル化、続く二酸化炭素によるカルボキシル化反応の開発2014

    • Author(s)
      田中 寛之、道上 健一、美多 剛、佐藤 美洋
    • Organizer
      日本薬学会北海道支部第141回例会
    • Place of Presentation
      札幌コンベンションセンター(札幌)
    • Year and Date
      2014-05-24
    • Related Report
      2014 Research-status Report
  • [Book] 二酸化炭素を用いた化学品製造技術2016

    • Author(s)
      美多 剛、佐藤 美洋
    • Total Pages
      14
    • Publisher
      S&T出版
    • Related Report
      2016 Annual Research Report
  • [Book] 二酸化炭素を用いた化学品製造技術2016

    • Author(s)
      美多 剛, 佐藤 美洋
    • Total Pages
      14
    • Publisher
      S&T出版株式会社
    • Related Report
      2015 Research-status Report
  • [Remarks] 北海道大学大学院薬学研究院・精密合成化学研究室

    • URL

      http://gouka.pharm.hokudai.ac.jp/FSC/jpn/page/top_page.htm

    • Related Report
      2016 Annual Research Report
  • [Remarks] 北海道大学大学院薬学研究院精密合成化学研究室

    • URL

      http://gouka.pharm.hokudai.ac.jp/FSC/jpn/page/top_page.htm

    • Related Report
      2014 Research-status Report

URL: 

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

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