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Application of the Diastereoselective Ketal Formation Reactions for the Organic Synthesis.

Research Project

Project/Area Number 15K07872
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Chemical pharmacy
Research InstitutionMusashino University

Principal Investigator

HIROYA Kou  武蔵野大学, 薬学研究所, 教授 (70192721)

Research Collaborator Takahashi Erina  
Nakamura Ayumi  
Fukuda Chiaki  
Hayakawa Emi  
Watanabe Akiho  
Ohkubo Mami  
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywordsジアステレオ選択的反応 / ケタール化反応 / 不斉第四級炭素 / 不斉四置換炭素 / 不斉合成 / 生物活性 / アルカロイド / 不斉ジヒドロキシル化反応
Outline of Final Research Achievements

The expansion of the substrates for the diastereoselective ketal formation reaction have been established as my primary object. The products of the diastereoselective ketal formation seem to be useful for synthetic organic chemistry. Therefore, I have arranged the synthesis of the important compounds as an optically active form for my second object.
Firstly, compounds having an aromatic ring and cinnamyl unit at C2 position of 1,3-cyclohexanedione have been synthesized and highly diastereoselective hemiketal and intermolecular ketal formation reaction have been achieved. Next, the asymmetric dihydroxylation reaction was examined utilizing commercially available reagents. As a result, the products which have almost 90%e.e. were afforded. Secondly, the conversion of the quaternary carbon center to chiral four substituted center was investigated and single lactam was obtained by Beckmann rearrangement. Synthetic studies of two natural products as optically active forms are now under way.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (15 results)

All 2017 2016 2015 Other

All Journal Article (5 results) (of which Peer Reviewed: 5 results,  Acknowledgement Compliant: 2 results) Presentation (8 results) Remarks (2 results)

  • [Journal Article] Simultaneous Functionalization and Cyclization of 2-Ethynylaniline Derivatives to Indoles2017

    • Author(s)
      Kou Hiroya, Shin Itoh, Kiyofumi Inamoto, Hiroki Shigehisa, and Takao Sakamoto
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 2 Pages: 920-933

    • DOI

      10.3987/com-16-s(s)60

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic Synthesis of Saturated Oxygen Heterocycles by Hydrofunctionalization of Unactivated Olefins: Unprotected and Protected Strategies2016

    • Author(s)
      Hiroki Shigehisa, Miki Hayashi, Haruna Ohkawa, Tsuyoshi Suzuki, Hiroki Okayasu, Mayumi Mukai, Ayaka Yamazaki, Ryohei Kawai, Harue Kikuchi, Yui Satoh, Akane Fukuyama, Kou Hiroya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 138 Issue: 33 Pages: 10597-10604

    • DOI

      10.1021/jacs.6b05720

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Co-Catalyzed Hydroarylation of Unactivated Olefins2016

    • Author(s)
      Hiroki Shigehisa, Takuya Ano, Hiroshi Honma, Kousuke Ebisawa, Kou Hiroya
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 15 Pages: 3622-3625

    • DOI

      10.1021/acs.orglett.6b01662

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Markovnikov-Selective Addition of Fluorous Solvents to Unactivated Olefins Using a Co Catalyst2016

    • Author(s)
      Hiroki Shigehisa, Harue Kikuchi, Kou Hiroya
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 64 Issue: 4 Pages: 371-374

    • DOI

      10.1248/cpb.c15-01024

    • NAID

      130005141025

    • ISSN
      0009-2363, 1347-5223
    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] The Revised Structure of Trichodermatide A2015

    • Author(s)
      Hiroki Shigehisa, Harue Kikuchi, Tsuyoshi Suzuki, Kou Hiroya
    • Journal Title

      European Journal of Organic Chemistry

      Volume: No.35 Issue: 35 Pages: 7670-7673

    • DOI

      10.1002/ejoc.201501281

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] キラルPHOX-パラジウム錯体を用いる動的速度論的光学分割反応の開発2016

    • Author(s)
      坂 貴穂・松崎里紗・岡部苑香・山田啓介・三宅裕美・重久浩樹・廣谷 功
    • Organizer
      第46回 複素環化学討論会
    • Place of Presentation
      石川県金沢市 金沢歌劇座
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
  • [Presentation] コバルト触媒を用いたオレフィンのヒドロ官能基化反応による含酸素複素環合成法2016

    • Author(s)
      重久浩樹・林 美希・大川陽菜・鈴木毅史・岡安弘樹・向 真由実・山崎彩香・川井涼平・佐藤優衣・福山 茜・廣谷 功
    • Organizer
      第46回 複素環化学討論会
    • Place of Presentation
      石川県金沢市 金沢歌劇座
    • Year and Date
      2016-09-26
    • Related Report
      2016 Research-status Report
  • [Presentation] コバルト錯体を用いた不活性オレフィンの分子内ヒドロアリール化反応2016

    • Author(s)
      阿野 卓哉,本間 皓,重久 浩樹,廣谷 功
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜 展示ホール AB(神奈川県・横浜市)
    • Year and Date
      2016-03-28
    • Related Report
      2015 Research-status Report
  • [Presentation] コバルト錯体を用いた不活性オレフィンの分子内ヒドロアルコキシル化・ヒドロアシルオキシ化反応2016

    • Author(s)
      林 美希,大川 陽菜,重久 浩樹,廣谷 功
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜 展示ホール AB(神奈川県・横浜市)
    • Year and Date
      2016-03-28
    • Related Report
      2015 Research-status Report
  • [Presentation] 海洋性ポリケチド Trichodermatide A の構造改訂2016

    • Author(s)
      菊池 陽媛,鈴木 毅史,重久 浩樹,廣谷 功
    • Organizer
      日本薬学会第136年会
    • Place of Presentation
      パシフィコ横浜 展示ホール AB(神奈川県・横浜市)
    • Year and Date
      2016-03-28
    • Related Report
      2015 Research-status Report
  • [Presentation] コバルト触媒を用いたオレフィンのヒドロアリール化反応2015

    • Author(s)
      阿野 卓哉,本間 皓,重久 浩樹,廣谷 功
    • Organizer
      第59回 日本薬学会関東支部大会
    • Place of Presentation
      日本大学薬学部(千葉県・船橋市)
    • Year and Date
      2015-09-12
    • Related Report
      2015 Research-status Report
  • [Presentation] コバルト触媒を用いたオレフィンの分子内ヒドロアルコキシル化反応とヒドロアシルオキシ化反応2015

    • Author(s)
      林 美希,大川 陽菜,重久 浩樹,廣谷 功
    • Organizer
      第59回 日本薬学会関東支部大会
    • Place of Presentation
      日本大学薬学部(千葉県・船橋市)
    • Year and Date
      2015-09-12
    • Related Report
      2015 Research-status Report
  • [Presentation] 海洋性天然物 Trichodermatide A の構造改訂2015

    • Author(s)
      菊池 陽媛,鈴木 毅史,重久 浩樹,廣谷 功
    • Organizer
      第59回 日本薬学会関東支部大会
    • Place of Presentation
      日本大学薬学部(千葉県・船橋市)
    • Year and Date
      2015-09-12
    • Related Report
      2015 Research-status Report
  • [Remarks] 教員情報

    • URL

      http://gyoseki.musashino-u.ac.jp/msuhp/KgApp?kyoinId=ymiygsoiggo

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
  • [Remarks] 武蔵野大学薬学部薬化学研究室ホームページ

    • URL

      http://www.musashino-u.ac.jp/facilities/pharmacy/yakka.html

    • Related Report
      2015 Research-status Report

URL: 

Published: 2015-04-16   Modified: 2019-03-29  

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