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Development of Methodology for Construction of Cyclic Skeletons Using NHC-Catalyzed Umpolung-Type Gamma-Addition Reaction

Research Project

Project/Area Number 15K18841
Research Category

Grant-in-Aid for Young Scientists (B)

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

Principal Investigator

Kuwano Satoru  千葉大学, 大学院理学研究院, 特任助教 (50733531)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2015: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords含窒素複素環式カルベン / 炭素環構築反応 / 極性転換 / シクロペンテン誘導体 / 転位反応 / ハロゲン結合 / インドール誘導体 / 不斉合成 / 酸塩基複合触媒 / 炭素環式化合物
Outline of Final Research Achievements

The cyclic skeleton is a component included in many biologically active compounds, and the development of a novel methodology for construction of cyclic skeletons is an important research topic leading to the creation of medicines, agricultural chemicals and the like. In this research, we aimed to develop a new method for the synthesis of carbocycles using N-heterocyclic carbene (NHC)-catalyzed umpolung-type γ addition reaction. As a result of various investigations, the γ addition reaction promoted by the addition of NHC proceeded and succeeded in the synthesis of the multiply substituted cyclopentene derivative. We also found that various indole derivatives can be synthesized by using halogen bond donating type iodine catalyst induced by iodination of NHC in the process of this investigation.

Report

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

    (29 results)

All 2018 2017 2016 Other

All Journal Article (9 results) (of which Peer Reviewed: 9 results,  Acknowledgement Compliant: 3 results,  Open Access: 1 results) Presentation (18 results) (of which Int'l Joint Research: 5 results,  Invited: 1 results) Remarks (2 results)

  • [Journal Article] Chiral Organic Base Catalyst with Halogen Bonding Donor Functionality: Asymmetric Mannich Reaction of Malononitrile with N-Boc Aldimines and Ketimines2018

    • Author(s)
      Satoru Kuwano, Takumi Suzuki, Yusei Hosaka, Takayoshi Arai
    • Journal Title

      Chem. Commun.

      Volume: 印刷中 Issue: 31 Pages: 3847-3850

    • DOI

      10.1039/c8cc00865e

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 2-Iodoimidazolinium Salt-catalyzed Friedel-Crafts Reaction: Synthesis of Bis(indolyl)methane Alkaloids2018

    • Author(s)
      Satoru Kuwano, Takumi Suzuki, Takayoshi Arai
    • Journal Title

      Heterocycles

      Volume: 印刷中 Issue: 1 Pages: 163-163

    • DOI

      10.3987/com-18-s(t)33

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Catalytic Asymmetric Mannich Reaction of Isatin-derived N-Boc Imines with Malononitrile by Bis(imidazolidine)-derived Pincer Rh Complex2017

    • Author(s)
      Arai, T.; Tosaka, T.; Kuwano, S.
    • Journal Title

      ChemistrySelect

      Volume: 2 Issue: 24 Pages: 7368-7371

    • DOI

      10.1002/slct.201701444

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] N-Heterocyclic Carbene-promoted [3+2] Cycloaddition of Allenyl Sulfone and Arylidenemalononitriles.2017

    • Author(s)
      Satoru Kuwano, Toshinobu Masuda, Koki Yamaguchi, Takayoshi Arai
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 1 Pages: 232-242

    • DOI

      10.3987/com-16-s(s)8

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chiral Bis(imidazolidine)iodobenzene (I-Bidine) Organocatalyst for Thiochromane Synthesis Using an Asymmetric Michael/Henry Reaction.2017

    • Author(s)
      Arai, T.; Suzuki, T.; Inoue, T.; Kuwano, S.
    • Journal Title

      Synlett

      Volume: 28 Issue: 01 Pages: 122-127

    • DOI

      10.1055/s-0036-1588614

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Site-selective Benzoin-type Cyclization of Unsymmetrical Dialdoses Catalyzed by N-Heterocyclic Carbenes for Divergent Cyclitol Synthesis.2017

    • Author(s)
      Bubwoon Kang, Yinli Wang, Satoru Kuwano, Yousuke Yamaoka, Kiyosei Takasu, Ken-ichi Yamada
    • Journal Title

      Chem. Commun.

      Volume: 印刷中 Issue: 32 Pages: 4469-4472

    • DOI

      10.1039/c7cc01191a

    • NAID

      120006650105

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] N-Heterocyclic Carbene Catalyzed Monoacylation of Vicinal Diols.2016

    • Author(s)
      Satoru Kuwano, Toshinobu Masuda
    • Journal Title

      Synthesis

      Volume: 48 Issue: 04 Pages: 573-578

    • DOI

      10.1055/s-0035-1560544

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Catalytic Asymmetric [3+2]-Cycloaddition for Stereodivergent Synthesis of Chiral Indolyl-pyrrolidines.2016

    • Author(s)
      Takayoshi Arai, Chihiro Tokumitsu, Tomoya Miyazaki, Satoru Kuwano, Atsuko Awata.
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 14 Issue: 5 Pages: 1831-1839

    • DOI

      10.1039/c5ob02278a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Oxa- and Azacycle-formation via Migrative Cyclization of Sulfonylalkynol and Sulfonylalkynamide with N-Heterocyclic Carbene.2016

    • Author(s)
      K. Yamada
    • Journal Title

      J. Org. Chem

      Volume: 81 Issue: 6 Pages: 2652-2664

    • DOI

      10.1021/acs.joc.6b00182

    • NAID

      120006881403

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] キラル芳香族ボロン酸/N-メチルイミダゾール触媒系を用いるシス1,2-ジオールの不斉非対称化反応2018

    • Author(s)
      保坂 悠成、 鍬野 哲、 荒井 孝義
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 2-ヨードイミダゾリニウム塩を用いる2-ビニルインドールの活性化による[4+2]環化付加反応2018

    • Author(s)
      鈴木 拓己、 鍬野 哲、 荒井 孝義
    • Organizer
      日本化学会 第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ヨウ素/窒素協同作用型触媒を用いるマロノニトリルのイミンへの不斉Mannich反応2018

    • Author(s)
      鍬野 哲、 鈴木 拓己、 荒井 孝義
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Chiral boronic acid-catalyzed asymmetric desymmetrization of meso-1,2-diols with sulfonyl chlorides2018

    • Author(s)
      Satoru Kuwano, Yusei Hosaka, Takayoshi Arai
    • Organizer
      The Second Symposium of Chiral Molecular Science and Technology in Chiba University -Advanced Materials Science, Biology & Nanophotonics in Chiba-
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Mannich Reaction Using Bifunctional Electron-Deficient Iodobenzene/tert-Amine Combined Catalyst2017

    • Author(s)
      Satoru Kuwano, Takumi Suzuki, Takayoshi Arai
    • Organizer
      日本化学会 第97春季年会 (2017)
    • Place of Presentation
      慶應義塾大学日吉キャンパス(神奈川県)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Chiral Bis(imidazolidine)iodobenzene (I-Bidine) Organocatalyst for Thiochromane Synthesis Using Asymmetric Michael/Henry Reaction2017

    • Author(s)
      SUZUKI, Takumi; INOUE, Takahiro; KUWANO, Satoru; ARAI, Takayoshi
    • Organizer
      日本化学会 第97春季年会 (2017)
    • Place of Presentation
      慶應義塾大学日吉キャンパス(神奈川県)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] ハロゲン結合ドナー/第三級アミン複合触媒を用いるマロノニトリルの不斉マンニッヒ反応2017

    • Author(s)
      鍬野 哲、鈴木 拓己、荒井 孝義
    • Organizer
      第6回JACI/GSCシンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] Development of Chiral Halogen-Bonding-Donor/Organic Base Combined Catalyst and Application to Asymmetric Mannich Reaction2017

    • Author(s)
      Satoru Kuwano, Takumi Suzuki, Takayoshi Arai
    • Organizer
      29th International Symposium on Chirality(Chirality 2017; ISCD-29)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ハロゲン結合ドナー/有機塩基複合触媒を用いる不斉Mannich反応の開発と構造活性相関2017

    • Author(s)
      鍬野 哲、鈴木 拓己、荒井 孝義
    • Organizer
      第20回ヨウ素学会シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] Catalytic Asymmetric Mannich Reaction of Isatin-derived N-Boc Imines with Malononitrile Using Halogen Bonding-onor/Organic Base Combined Catalyst2017

    • Author(s)
      Satoru Kuwano, Takumi Suzuki, Takayoshi Arai
    • Organizer
      HALCHEM VIII
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Dimerization of 2-Vinylindoles Catalysed by Cationic Halogen-Bonding Donors2017

    • Author(s)
      Takumi Suzuki, Satoru Kuwano, Takayoshi Arai
    • Organizer
      HALCHEM VIII
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ヨウ素/窒素協同作用型触媒を用いる不斉Mannich反応2017

    • Author(s)
      鍬野 哲、鈴木 拓己、荒井 孝義
    • Organizer
      第44回有機典型元素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] キラルボロン酸触媒を用いた環状1,2-ジオールの不斉スルホニル化反応2017

    • Author(s)
      保坂 悠成、 鍬野 哲、 荒井 孝義
    • Organizer
      第74回有機合成化学協会関東支部シンポジウム(新潟シンポジウム)
    • Related Report
      2017 Annual Research Report
  • [Presentation] NHC触媒を用いる隣接ジオール類のモノアシル化反応の開発2016

    • Author(s)
      鍬野 哲,増田 寿伸
    • Organizer
      日本化学会 第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス(京都府・京田辺市)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Exploration of Secondary Amine Organocatalyst Using Solid-Phase Catalysis/CD HTS for Asymmetric Mannich Reaction2016

    • Author(s)
      Satoru Kuwano, Takahiro Inoue, Takayoshi Arai
    • Organizer
      The 1st Symposium of Chiral Molecular Science & Technology in Chiba University
    • Place of Presentation
      千葉大学西千葉キャンパス(千葉県・千葉市)
    • Year and Date
      2016-02-29
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] 協調作用を有する第二級アミン不斉有機触媒の開発2016

    • Author(s)
      鍬野 哲,鈴木 拓己,井上 貴博,荒井 孝義
    • Organizer
      「有機分子触媒による未来型分子変換」第6回公開シンポジウム
    • Place of Presentation
      大阪科学技術センター(大阪府・大阪市)
    • Year and Date
      2016-01-22
    • Related Report
      2015 Research-status Report
  • [Presentation] NHC触媒を用いる速度論的光学分割及びモノアシル化反応の開発2016

    • Author(s)
      鍬野 哲
    • Organizer
      関東支部若手研究者のためのセミナー
    • Place of Presentation
      東京大学薬学系総合研究棟2階講堂(東京都)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Chiral Bis(imidazolidine)iodobenzene (I-Bidine) Organocatalyst for Thiochromane Synthesis Using Asymmetric Michael/Henry Reaction2016

    • Author(s)
      鈴木拓己、井上貴博、鍬野哲、荒井孝義
    • Organizer
      第19回ヨウ素学会シンポジウム
    • Place of Presentation
      千葉大学西千葉キャンパス総合校舎(千葉県)
    • Related Report
      2016 Research-status Report
  • [Remarks] 千葉大学 有機合成化学研究室

    • URL

      http://synthesis.chem.chiba-u.jp/

    • Related Report
      2017 Annual Research Report
  • [Remarks] 千葉大学大学院理学研究科 化学コース 有機合成化学研究室

    • URL

      http://synthesis.chem.chiba-u.jp/

    • Related Report
      2016 Research-status Report

URL: 

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

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