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Development of Enantioselective Acylation Based on Hydrogen-Bonding Strategy

Research Project

Project/Area Number 17K17903
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Organic chemistry
Research InstitutionOkayama University

Principal Investigator

Mandai Hiroki  岡山大学, 自然科学研究科, 特任助教 (60534427)

Project Period (FY) 2017-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2018: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2017: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywords有機分子触媒 / 求核触媒 / アシル化 / エナンチオ選択的 / N,N-ジメチル-4-アミノピリジン / 1,3-ジオール / 糖 / 不斉求核触媒 / エナンチオ選択的アシル化 / 位置選択的アシル化 / グリセロール / ポリオール / DMAP / 速度論的光学分割 / 光学活性化合物 / 不斉触媒反応
Outline of Final Research Achievements

With an optically active DMAP with tertiary alcohols moiety developed by our group, we examined enantioselective acylation of more complexed polyols. When the reaction was carried out using linear or cyclic 1,3-diol or 1,2,3-triol derivatives, the target monoacylated products were successfully obtained in high yield with high enantioselectivity. We also examined the regioselective acylation of carbohydrates for the synthesis of chiral building with high synthetic utility value. As a result of various control experiments, it was revealed that this reaction had high reaction acceleration effect and enantioselectivity (or regioselectivity) by hydrogen bonding.

Academic Significance and Societal Importance of the Research Achievements

本研究成果は,医薬品,農薬,天然物などの生物活性化合物合成に利用できるキラルビルディングを迅速かつ効率的に合成できる方法であり,医薬品や農薬などのファインケミカルの分野に大きく波及するものと期待している.

Report

(3 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • Research Products

    (31 results)

All 2019 2018 2017 Other

All Journal Article (14 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 14 results,  Open Access: 1 results) Presentation (13 results) (of which Invited: 1 results) Book (1 results) Remarks (3 results)

  • [Journal Article] Iodide-Mediated or Iodide-Catalyzed Demethylation and Friedel-Crafts C-H Borylative Cyclization Leading to Thiophene-Fused 1,2-Oxaborine Derivatives2019

    • Author(s)
      Shigemori Keisuke、Watanabe Momoka、Kong Julie、Mitsudo Koichi、Wakamiya Atsushi、Mandai Hiroki、Suga Seiji
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 7 Pages: 2171-2175

    • DOI

      10.1021/acs.orglett.9b00485

    • NAID

      120006808071

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Efficient Synthesis and Properties of [1]Benzothieno[3,2-b]thieno[2,3-d]furans and [1]Benzothieno[3,2-b]thieno[2,3-d]thiophenes2018

    • Author(s)
      Kurimoto Yuji、Mitsudo Koichi、Mandai Hiroki、Wakamiya Atsushi、Murata Yasujiro、Mori Hiroki、 Nishihara Yasushi、Suga Seiji
    • Journal Title

      Asian Journal of Organic Chemistry

      Volume: 7 Issue: 8 Pages: 1635-1641

    • DOI

      10.1002/ajoc.201800270

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent topics in enantioselective acyl transfer reactions with dialkylaminopyridine-based nucleophilic catalysts2018

    • Author(s)
      Mandai Hiroki、Fujii Kazuki、Suga Seiji
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Issue: 19 Pages: 1787-1803

    • DOI

      10.1016/j.tetlet.2018.03.016

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu/Fe/O=PPh3-Catalyzed Etherification for the Synthesis of Aryl 3-Benzo[b]thienyl Ethers2018

    • Author(s)
      Mitsudo Koichi、Asada Takuya、Inada Tomohiro、Kurimoto Yuji、Mandai Hiroki、Suga Seiji
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 8 Pages: 1044-1047

    • DOI

      10.1246/cl.180425

    • NAID

      130007430998

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dynamic Kinetic Resolution of Azlactones by a Chiral N,N-Dimethyl-4-aminopyridine Derivative Containing a 1,1′-Binaphthyl Unit: Importance of Amide Groups2018

    • Author(s)
      Mandai Hiroki、Hongo Kohei、Fujiwara Takuma、Fujii Kazuki、Mitsudo Koichi、Suga Seiji
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 16 Pages: 4811-4814

    • DOI

      10.1021/acs.orglett.8b01960

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Desymmetrization of 1,3-Diols by a Chiral DMAP Derivative2018

    • Author(s)
      Mandai Hiroki、Ashihara Kosuke、Mitsudo Koichi、Suga Seiji
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 11 Pages: 1360-1363

    • DOI

      10.1246/cl.180697

    • NAID

      130007504936

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Properties of Dithieno-Fused 1,4-Azaborine Derivatives2018

    • Author(s)
      Mitsudo Koichi、Shigemori Keisuke、Mandai Hiroki、Wakamiya Atsushi、Suga Seiji
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 22 Pages: 7336-7340

    • DOI

      10.1021/acs.orglett.8b03316

    • NAID

      120006765098

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Fungal metabolite (+)-terrein suppresses IL-6/sIL-6R-induced CSF1 secretion by inhibiting JAK1 phosphorylation in human gingival fibroblasts2018

    • Author(s)
      Satoshi Yamamoto, Kazuhiro Omori, Hiroki Mandai, Masaaki Nakayama, Saki Nakagawa, Hiroya Kobayashi, Tadashi Kunimine, Hiroshi Yoshimura, Kyosuke Sakaida, Hidefumi Sako, Soichiro Ibaragi, Tadashi Yamamoto, Hiroshi Maeda, Seiji Suga, and Shogo Takashiba
    • Journal Title

      Heliyon

      Volume: 4 Issue: 11 Pages: e00979-e00979

    • DOI

      10.1016/j.heliyon.2018.e00979

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Enantioselective Acyl Migration Reactions of Furanyl Carbonates with Chiral DMAP Derivatives2018

    • Author(s)
      Fujii Kazuki、Mitsudo Koichi、Mandai Hiroki、Korenaga Toshinobu、Suga Seiji
    • Journal Title

      Chemistry - A European Journal

      Volume: 26 Issue: 9 Pages: 2208-2212

    • DOI

      10.1002/chem.201806050

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Desymmetrization of meso-1,2-Diols by a Chiral N,N-4-Dimethylaminopyridine Derivative Containing a 1,1′-Binaphthyl Unit: Importance of the Hydroxy Groups2017

    • Author(s)
      Mandai Hiroki、Yasuhara Hiroshi、Fujii Kazuki、Shimomura Yukihito、Mitsudo Koichi、Suga Seiji
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 82 Issue: 13 Pages: 6846-6856

    • DOI

      10.1021/acs.joc.7b00992

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Magnetic Attachment of Lipase Immobilized on Bacteriogenic Iron Oxide Inside a Microtube Reactor for the Kinetic Resolution of Secondary Alcohols2017

    • Author(s)
      Kyoko Mandai, Takehiro Fukuda, Yuki Miyazaki, Hideki Hashimoto, Hiroki Mandai, Tadashi Ema, Jun Takada, and Seiji Suga
    • Journal Title

      Synlett

      Volume: 28 Issue: 07 Pages: 805-810

    • DOI

      10.1055/s-0036-1589953

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 3-Benzo[b]thienyl 3-Thienyl Ether via an Addition-Elimination Reaction and Its Transformation to an Oxygen-Fused Dithiophene Skeleton: Synthesis and Properties of Benzodithienofuran and Its π-Extended Derivatives2017

    • Author(s)
      Mitsudo Koichi、Kurimoto Yuji、Mandai Hiroki、Suga Seiji
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 11 Pages: 2821-2824

    • DOI

      10.1021/acs.orglett.7b00969

    • NAID

      120006765097

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rh-Catalyzed Dehydrogenative Cyclization Leading to Benzosilolothiophene Derivatives via Si-H/C-H Bond Cleavage2017

    • Author(s)
      Mitsudo Koichi、Tanaka Seiichi、Isobuchi Ryota、Inada Tomohiro、Mandai Hiroki、Korenaga Toshinobu、Wakamiya Atsushi、Murata Yasujiro、Suga Seiji
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 10 Pages: 2564-2567

    • DOI

      10.1021/acs.orglett.7b00878

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Development of Efficient and Effective Rate Acceleration Systems in Organocatalysis2017

    • Author(s)
      Mandai Hiroki、Fujii Kazuki、Suga Seiji
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 75 Issue: 6 Pages: 632-649

    • DOI

      10.5059/yukigoseikyokaishi.75.632

    • NAID

      130006903253

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 光学活性DMAP誘導体を用いた糖類の位置選択的アシル化反応2018

    • Author(s)
      山本知哉,阿部健幸,萬代大樹,菅 誠治
    • Organizer
      第48回 複素環化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 高活性な光学活性DMAP誘導体を用いる軸性キラル化合物の速度論的光学分割反応2018

    • Author(s)
      萬代大樹,松浦悠一郎,竹田直史,菅 誠治
    • Organizer
      第11回有機触媒シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光学活性DMAP誘導体を用いるキラルビアリール化合物の速度論的光学分割2018

    • Author(s)
      松浦悠一郎,中村亮太,竹田直史,萬代大樹,菅 誠治
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光学活性DMAP誘導体を用いるメソ-1,3-ジオールの不斉アシル化反応による非対称化2018

    • Author(s)
      広中 翼,萬代大樹,菅 誠治
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光学活性DMAP 誘導体を用いるアシル化反応(1): 3-ヒドロキシ-3-置換-オキシインドール類の速度論的光学分割2018

    • Author(s)
      萬代大樹,塩本龍平,菅 誠治
    • Organizer
      日本化学会第98春季年会,日本大学船橋キャンパス
    • Related Report
      2017 Research-status Report
  • [Presentation] 光学活性DMAP 誘導体を用いるアシル化反応(2): 1,3-ジオール の非対称化反応2018

    • Author(s)
      芦原宏介,萬代大樹,菅 誠治
    • Organizer
      日本化学会第98春季年会,日本大学船橋キャンパス
    • Related Report
      2017 Research-status Report
  • [Presentation] 光学活性DMAP誘導体を用いるアシル化反応(3): 糖類の位置選 択的アシル化反応2018

    • Author(s)
      山本知哉,阿部健幸,萬代大樹,菅 誠治
    • Organizer
      日本化学会第98春季年会,日本大学船橋キャンパス
    • Related Report
      2017 Research-status Report
  • [Presentation] 光学活性DMAP誘導体を用いるアズラクトンの動的速度論的光学分割反応の開発2017

    • Author(s)
      本郷晃平,萬代大樹,菅 誠治
    • Organizer
      第47回複素環化学討論会,高知県民文化ホール(高知)
    • Related Report
      2017 Research-status Report
  • [Presentation] エナンチオ選択的なアシル化によるmeso-1,2-ジオール類の非対称化反応2017

    • Author(s)
      萬代大樹,安原 宏,藤居一輝,下村征史,菅 誠治
    • Organizer
      第47回複素環化学討論会,高知県民文化ホール(高知)
    • Related Report
      2017 Research-status Report
  • [Presentation] Development of Extremely Active Nucleophilic Catalysts for Enantioselective Transformations2017

    • Author(s)
      Hiroki Mandai
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017), Ho Chi Minh City, Vietnam
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] ジオール類のエナンチオ選択的モノアシル化反応の開発2017

    • Author(s)
      萬代大樹,安原宏,藤居一輝,下村征史,菅 誠治
    • Organizer
      日本プロセス化学会2017サマーシンポジウム,大阪国際交流センター(大阪)
    • Related Report
      2017 Research-status Report
  • [Presentation] ベンゾフラノン類のエナンチオ選択的 Steglich 型転位反応の開発2017

    • Author(s)
      藤居一輝,萬代大樹,菅 誠治
    • Organizer
      日本プロセス化学会2017サマーシンポジウム,大阪国際交流センター(大阪)
    • Related Report
      2017 Research-status Report
  • [Presentation] 高活性な光学活性DMAP誘導体を用いるジオール類および糖類のアシル化反応2017

    • Author(s)
      萬代大樹,芦原宏介,山本知哉,阿部健幸,藤居一輝,菅 誠治
    • Organizer
      第10回有機触媒シンポジウム,東北大学(宮城)
    • Related Report
      2017 Research-status Report
  • [Book] 有機分子触媒の開発と工業利用(分担執筆)2018

    • Author(s)
      萬代大樹,菅 誠治
    • Total Pages
      330
    • Publisher
      シーエムシー出版
    • ISBN
      9784781313238
    • Related Report
      2017 Research-status Report
  • [Remarks] 合成プロセス化学研究室:菅研究室

    • URL

      http://achem.okayama-u.ac.jp/reacteng/

    • Related Report
      2018 Annual Research Report
  • [Remarks] 萬代大樹 (Hiroki Mandai): Personal Website

    • URL

      http://mandai.wpblog.jp

    • Related Report
      2018 Annual Research Report 2017 Research-status Report
  • [Remarks] 合成プロセス化学研究室

    • URL

      http://achem.okayama-u.ac.jp/reacteng/

    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2020-03-30  

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