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Development of Catalytic Asymmetric Electrocyclic Reaction by Twisting Substrate

Research Project

Project/Area Number 16K08154
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

Harada Shinji  千葉大学, 大学院薬学研究院, 助教 (10451759)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2018: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords不斉触媒 / らせん状変形 / ニッケル触媒 / ヒドロカルバゾール / インドール / 7員環合成 / 8員環合成 / シクロオクタインドール / インデノール / インデセン / 銅触媒 / 合成化学 / 電子環状反応 / 多段階反応
Outline of Final Research Achievements

The target of this project was the development of new synthetic methods for the construction of carbocycles. Carbocycles are seen in the structure of clinical drugs and biologically active compounds.
We have developed our original chiral nickel catalyst which twists the coordinated molecule. With the use of this catalyst and its structural information, we achieved stereoselective construction of 6-membered ring. It was applied to the enantioselective synthesis of carbazole skeletons.
We developed the stereoselective construction of 5-membered ring by using chiral copper catalyst. We also achieved the indium-catalyzed 7-membered ring formation. 8-Membered ring construction was just developed by using ytterbium catalyst, and we are now preparing the manuscript for publication.

Academic Significance and Societal Importance of the Research Achievements

今回の成果は分子のらせん状ねじれを利用した新しい環状分子の構築法の開発である。らせん状ねじれによって環状構造を形成しやすくするという方法論が広く一般的に有機合成に利用できる可能性を広めた。また、一般的に構築が難しいとされる7員環以上の大きさの環構築にも取り組み、7員環と8員環構築法を開発した。いずれも共通の5炭素ユニットを原料として用いており、それぞれ2炭素もしくは3炭素ユニットと組み合わせた。組み合わせるユニットの炭素数を変えることで様々な大きさの環への適用拡大が期待できる。有機合成化学上の意義に留まらず、医薬化学への貢献にも繋がる成果である。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (38 results)

All 2019 2018 2017 2016 Other

All Journal Article (6 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 6 results,  Acknowledgement Compliant: 2 results) Presentation (30 results) (of which Int'l Joint Research: 7 results,  Invited: 3 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results) (of which Overseas: 1 results)

  • [Journal Article] Enantioselective carbonyl-ene-type cyclization of α-ketoester and 2-substituted vinylsilane catalyzed by a chiral Cu-BOX complex2018

    • Author(s)
      Homma Haruka、Harada Shinji、Nishida Atsushi
    • Journal Title

      Tetrahedron Letters

      Volume: 59 Issue: 28 Pages: 2755-2758

    • DOI

      10.1016/j.tetlet.2018.06.001

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cyclohepta[b]indole Synthesis through [5 + 2] Cycloaddition: Bifunctional Indium(III)-Catalyzed Stereoselective Construction of 7-Membered Ring Fused Indoles2018

    • Author(s)
      Takeda Takuya、Harada Shinji、Okabe Akito、Nishida Atsushi
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 83 Issue: 19 Pages: 11541-11551

    • DOI

      10.1021/acs.joc.8b01407

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Total Synthesis of Carbazomycins A and B2018

    • Author(s)
      Wu Siyuan、Harada Shinji、Morikawa Takahiro、Nishida Atsushi
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 66 Issue: 2 Pages: 178-183

    • DOI

      10.1248/cpb.c17-00851

    • NAID

      130006328169

    • ISSN
      0009-2363, 1347-5223
    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective total synthesis of a natural hydrocarbazolone alkaloid, identification of its stereochemistry, and revision of its spectroscopic data2017

    • Author(s)
      Wu Siyuan、Harada Shinji、Morikawa Takahiro、Nishida Atsushi
    • Journal Title

      Tetrahedron: Asymmetry

      Volume: 28 Issue: 8 Pages: 1083-1088

    • DOI

      10.1016/j.tetasy.2017.07.005

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalytic and Enantioselective Diels-Alder Reaction of Silyloxydiene That Incorporates a Pyrrolidine Ring, and Its Application to the Construction of Chiral Tri- and Tetracyclic Skeletons2017

    • Author(s)
      Shinji Harada, Saki Nakashima, Wataru Yamada, Takahiro Morikawa, Atsushi Nishida
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 2 Pages: 872-893

    • DOI

      10.3987/com-16-s(s)56

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Construction of Optically Active Isotwistanes and Aminocyclitols Using Chiral Cyclohexadiene as a Common Intermediate2016

    • Author(s)
      Shinji Harada, Kexin Li, Ryuto Kino, Takuya Takeda, Chia-Hsien Wu, Shiharu Hiraoka, and Atsushi Nishida,
    • Journal Title

      Chemical and Pharmaceutical Bulletin

      Volume: 64 Issue: 10 Pages: 1474-1483

    • DOI

      10.1248/cpb.c16-00431

    • NAID

      130005598056

    • ISSN
      0009-2363, 1347-5223
    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Presentation] 六配位キラル配位子を用いた新規ランタノイド錯体による触媒的不斉Diels-Alder反応2019

    • Author(s)
      關野詩穂里、大石若奈、中嶋早紀、原田真至、西田篤司
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 可視光酸化還元触媒を用いた三置換オレフィンの酸素酸化反応の開発2019

    • Author(s)
      松田大樹、原田真至、森川貴裕、西田篤司
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 分子間[5+3]環化付加反応によるインドール縮環型八員環構築法の開発2019

    • Author(s)
      岡部朗人、原田真至、竹田拓矢、西田篤司
    • Organizer
      日本薬学会第139年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 複素環融合型シロキシジエンの触媒的不斉Diels-Alder反応の開発2018

    • Author(s)
      原田真至、中嶋早紀、斉藤博則、西田篤司
    • Organizer
      モレキュラー・キラリティー シンポジウム 2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 6配位キラルシッフ塩基配位子を用いた希土類錯体による触媒的不斉Diels-Alder反応2018

    • Author(s)
      原田真至、中嶋早紀、西田篤司
    • Organizer
      第34回希土類討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 可視光酸化還元触媒を利用した三置換オレフィンの酸素酸化反応の開発2018

    • Author(s)
      松田大樹、原田真至、森川貴裕、西田篤司
    • Organizer
      第75回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 分子間環化付加反応によるインドール縮環型七員環及び八員環構築法の開発2018

    • Author(s)
      岡部朗人、竹田拓矢、原田真至、西田篤司
    • Organizer
      第75回有機合成化学協会関東支部シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] Catalytic and Enantioselective Construction of Heterocycle-fused Carbocycles2018

    • Author(s)
      Shinji Harada, Hironori Saito, Saki Nakashima, Takuya Takeda, Atsushi Nishida
    • Organizer
      16th Belgian Organic Synthesis Symposium (BOSS XVI)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Catalytic and Enantioselective Diels-Alder Reaction of Acid-Sensitive Siloxydienes2018

    • Author(s)
      Shinji Harada, Takahiro Morikawa, Saki Nakashima, Atsushi Nishida
    • Organizer
      International Congress on Pure & Applied Chemistry Langkawi (ICPAC Langkawi) 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Cyclohepta[b]indole Synthesis Through [5+2] Cycloaddition2018

    • Author(s)
      Atsushi Nishida, Takuya Takeda, Akito Okabe, Shinji Harada
    • Organizer
      The 13th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-13)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 複素環融合型シロキシジエンの触媒的不斉Diels-Alder反応の開発2018

    • Author(s)
      中嶋早紀、山田航、森川貴裕、原田真至、西田篤司
    • Organizer
      日本薬学会第138年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 電子豊富ジエンとマレイミド誘導体の触媒的不斉Diels-Alder反応の開発2018

    • Author(s)
      大石若奈、坂本駿、江森皓亮、池田亮平、原田真至、西田篤司
    • Organizer
      日本薬学会第138年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 酸素分子を用いた可視光酸化還元触媒によるスチレン誘導体の酸化反応の開発2018

    • Author(s)
      松田大樹、原田真至、森川貴裕、西田篤司
    • Organizer
      日本薬学会第138年会
    • Related Report
      2017 Research-status Report
  • [Presentation] (-)-minovincineの全合成と可視光酸化還元触媒を用いる二重結合修飾反応の開発2017

    • Author(s)
      森川貴裕、原田真至、西田篤司
    • Organizer
      日本薬学会第137年会
    • Place of Presentation
      仙台国際センター・東北大学
    • Year and Date
      2017-03-25
    • Related Report
      2016 Research-status Report
  • [Presentation] Enantioselective Diels-Alder Reaction Using Chiral Holmium Complex, and the Construction of Nitrogen-Containing Polycyclic Skeleton2017

    • Author(s)
      Saki Nakashima, Wataru Yamada, Takahiro Morikawa, Shinji Harada, Atsushi Nishida
    • Organizer
      日本化学会第97春季年会2017
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Catalytic and Enantioselective Nazarov Cyclization through a Chiral Dinuclear Nickel Complex2017

    • Author(s)
      Shinji Harada, Takuya Takeda, Atsushi Nishida
    • Organizer
      日本化学会第97春季年会2017
    • Place of Presentation
      慶應義塾大学
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] α-ケトエステルの活性化を利用した不斉四置換炭素を含むインデノール環構築反応の開発2017

    • Author(s)
      本間榛花、原田真至、西田篤司
    • Organizer
      第73回有機合成化学協会関東支部シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] ホルミウム-チオ尿素触媒を用いる多置換複素環の不斉合成法の開発2017

    • Author(s)
      原田真至、森川貴裕、中嶋早紀、西田篤司
    • Organizer
      第33回希土類討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 分子間環化付加反応によるインドール縮環型七員環および八員環構築法の開発2017

    • Author(s)
      岡部朗人、竹田拓矢、森川貴裕、原田真至、西田篤司
    • Organizer
      第34回有機合成化学セミナー
    • Related Report
      2017 Research-status Report
  • [Presentation] Danishefskyジエンとマレイミド誘導体による触媒的不斉Diels-Alder反応の開発2017

    • Author(s)
      大石若奈、江森皓亮、坂本駿、池田亮平、原田真至、西田篤司
    • Organizer
      第34回有機合成化学セミナー
    • Related Report
      2017 Research-status Report
  • [Presentation] α-ケトチオエステルの活性化を基盤とする触媒的不斉Diels-Alder反応の開発2017

    • Author(s)
      斉藤博則、原田真至、本間榛花、西田篤司
    • Organizer
      第61回日本薬学会関東支部大会
    • Related Report
      2017 Research-status Report
  • [Presentation] A New Chiral Ni Catalyst Promotes Asymmetric Nazarov and Diels-Alder Reactions2017

    • Author(s)
      Atsushi Nishida, Takuya Takeda, Hironori Saito, Haruka Homma, Shinji Harada
    • Organizer
      The 7th Sino-Japanese Symposium on Organic Chemistry for Young Scientists
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 不斉カルボニルーエン反応による四置換炭素を含む光学活性インデノール合成法の開発2017

    • Author(s)
      本間榛花、原田真至、西田篤司
    • Organizer
      第7回CSJ化学フェスタ2017
    • Related Report
      2017 Research-status Report
  • [Presentation] α-ケトエステルの活性化を鍵とする五員環構築反応の開発2016

    • Author(s)
      本間榛花、竹田拓矢、原田真至、西田篤司
    • Organizer
      第72回有機合成化学協会関東支部新潟シンポジウム
    • Place of Presentation
      新潟薬科大学
    • Year and Date
      2016-11-26
    • Related Report
      2016 Research-status Report
  • [Presentation] 複素環融合型ジエンを用いた触媒的不斉Diels-Alder反応の開発と含窒素多環性骨格の構築2016

    • Author(s)
      中嶋早紀、山田航、森川貴裕、原田真至、西田篤司
    • Organizer
      第72回有機合成化学協会関東支部新潟シンポジウム
    • Place of Presentation
      新潟薬科大学
    • Year and Date
      2016-11-26
    • Related Report
      2016 Research-status Report
  • [Presentation] ホルミウム-チオ尿素触媒を用いるヒドロカルバゾール不斉合成法の開発と天然物合成への展開2016

    • Author(s)
      森川貴裕、原田真至、西田篤司
    • Organizer
      第6回CSJフェスタ2016
    • Place of Presentation
      タワーホール船堀
    • Year and Date
      2016-11-14
    • Related Report
      2016 Research-status Report
  • [Presentation] 触媒的Diels-Alder反応を用いるカルバゾマイシン類の全合成研究2016

    • Author(s)
      呉思遠、原田真至、西田篤司
    • Organizer
      第21回天然薬物の開発と応用シンポジウム
    • Place of Presentation
      千葉大学
    • Year and Date
      2016-10-27
    • Related Report
      2016 Research-status Report
  • [Presentation] ケトエステルの活性化を鍵とする環構築反応の開発2016

    • Author(s)
      本間榛花、竹田拓矢、原田真至、西田篤司
    • Organizer
      第33回有機合成化学セミナー
    • Place of Presentation
      ニセコ
    • Year and Date
      2016-09-06
    • Related Report
      2016 Research-status Report
  • [Presentation] 複素環融合型ジエンを用いた触媒的不斉Diels-Alder反応の開発と含窒素四巻性骨格の合成2016

    • Author(s)
      中嶋早紀、山田航、森川貴裕、原田真至、西田篤司
    • Organizer
      第33回有機合成化学セミナー
    • Place of Presentation
      ニセコ
    • Year and Date
      2016-09-06
    • Related Report
      2016 Research-status Report
  • [Presentation] Development of Chiral Holmium Catalyst for Enantioselective Diels-Alder Reaction2016

    • Author(s)
      Saki Nakashima, Wataru Yamada, Takahiro Morikawa, Shinji Harada, and Atsushi Nishida
    • Organizer
      International Symposium on Lanthanide Coordination Chemistry 2016
    • Place of Presentation
      Aoyama Gakuin University
    • Year and Date
      2016-06-04
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Remarks] 薬品合成化学研究室ホームページ

    • URL

      http://www.p.chiba-u.jp/lab/gousei/index.html

    • Related Report
      2017 Research-status Report 2016 Research-status Report
  • [Patent(Industrial Property Rights)] 光学活性希土類錯体、この錯体からなる不斉触媒、及び、この不斉触媒を用いた光学活性有機化合物の製造方法2019

    • Inventor(s)
      西田篤司、原田真至、中嶋早紀
    • Industrial Property Rights Holder
      西田篤司、原田真至、中嶋早紀
    • Industrial Property Rights Type
      特許
    • Filing Date
      2019
    • Related Report
      2018 Annual Research Report
    • Overseas

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Published: 2016-04-21   Modified: 2020-03-30  

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