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Generation of Chirality Triggered by Sunlight Irradiation and Development of New Asymmetric Catalysts

Research Project

Project/Area Number 24655025
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeSingle-year Grants
Research Field Organic chemistry
Research InstitutionChiba University

Principal Investigator

SAKAMOTO Masami  千葉大学, 工学(系)研究科(研究院), 教授 (00178576)

Project Period (FY) 2012-04-01 – 2014-03-31
Project Status Completed (Fiscal Year 2013)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2013: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2012: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywords有機光化学 / 有機結晶 / 不斉合成 / 有機合成化学
Research Abstract

A new methodology of effective asymmetric synthesis starting from achiral materials without external chiral source was developed. Irradiation of achiral chromonecarboxylic esters in solution afforded crystalline chromone dimers in optically active form. The mechanism of generation of chirality was clarified and the optical purity of the products was attained 80% by examining conditions. Furthermore, the optically active products were utilized as ligands for catalytic asymmetric synthesis using organometallic compounds. Moreover, this methodology was expanded to a new asymmetric synthesis, and the absolute asymmetric synthesis of isoindolinones with high optical purity was achieved by a reaction of 2-benzoylbenzoic acid derivative with amines.

Report

(3 results)
  • 2013 Annual Research Report   Final Research Report ( PDF )
  • 2012 Research-status Report
  • Research Products

    (46 results)

All 2014 2013 2012 Other

All Journal Article (10 results) (of which Peer Reviewed: 10 results) Presentation (35 results) (of which Invited: 4 results) Remarks (1 results)

  • [Journal Article] Asymmetric Transformation by Dynamic Crystallization of Achiral Succinimides2013

    • Author(s)
      Shoko Hachiya, Yoshio Kasashima, Fumitoshi, Yagishita, Takashi Mino, Hyuma Masu, Masami Sakamoto
    • Journal Title

      Chem. Commun

      Volume: 49 Issue: 42 Pages: 4776-4778

    • DOI

      10.1039/c3cc41678j

    • Related Report
      2013 Annual Research Report 2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Chiral Symmetry Breaking of Axially Chiral Nicotinamide by Crystallization from the Melt2013

    • Author(s)
      Fumitoshi Yagishita, Kazuma Okamoto, Norifumi Kamataki, Shota Kanno, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
    • Journal Title

      Chemistry Letters

      Volume: 42 Issue: 12 Pages: 1508-1510

    • DOI

      10.1246/cl.130796

    • NAID

      130004867852

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Deracemization of Axially Chiral Nicotinamides by Dynamic Salt Formation with Enantiopure DBTA2013

    • Author(s)
      Fumitoshi Yagishita, Norifumi Kamataki, Kazuma Okamoto, Shota Kanno, Takashi Mino, Hyuma Masu, Masami Sakamoto
    • Journal Title

      Molecules

      Volume: 18 Issue: 11 Pages: 14430-14447

    • DOI

      10.3390/molecules181114430

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Copper- catalyzed asymmetric propargylic amination of propargylic acetates with amines using BICMAP2013

    • Author(s)
      Takashi Mino, Hiroyuki Taguchi, Masatoshi Hashimoto, Masami Sakamoto
    • Journal Title

      Tetrahedron : Asymmetry

      Volume: 24 Issue: 23 Pages: 1520-1523

    • DOI

      10.1016/j.tetasy.2013.10.007

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Mizoroki-Heck Type Reaction with Aryliodine Diacetates Using Hydrazone Ligand2013

    • Author(s)
      Takashi Mino, Kohei Watanabe, Taichi Abe, Taketo Kogure, Masami Sakamoto
    • Journal Title

      Heterocycles

      Volume: 87 Issue: 10 Pages: 2015-2021

    • DOI

      10.3987/com-13-12786

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed asymmetric allylic alkylation ofindoles by C-N bond axially chiralphosphine ligands2013

    • Author(s)
      Takashi Mino, Miho Ishikawa, Kenji Nishikawa, Kazuya Wakui, Masami Sakamoto
    • Journal Title

      Tetrahedron:Asymm.

      Volume: Vol. 24(印刷中) Issue: 8 Pages: 499-504

    • DOI

      10.1016/j.tetasy.2013.03.008

    • Related Report
      2013 Annual Research Report 2013 Final Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-catalyzed allylic arylation of allylic ethers with arylboronic acids using hydrazone ligands2013

    • Author(s)
      Takashi Mino, Takaehito Kogure, Taichi Abe, T. Koizumi, Tsutomu Fujita, Masami Sakamoto
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2013 Issue: 8 Pages: 1501-1505

    • DOI

      10.1002/ejoc.201201276

    • Related Report
      2013 Annual Research Report 2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Photocycloaddition Reaction of Methyl 2-and 3-Chromonecarboxylates with Various Alkenes2012

    • Author(s)
      Masami Sakamoto, et al
    • Journal Title

      Res. Chem. Intermed

      Volume: 39 Issue: 1 Pages: 385-395

    • DOI

      10.1007/s11164-012-0656-0

    • Related Report
      2013 Annual Research Report 2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Total Spontaneous Resolution by Deracemization of Isoindolinones2012

    • Author(s)
      Fumitoshi Yagishita, Hiroki Ishikawa, Tatsuo Onuki, Shoko Hachiya, Takashi Mino, Masami Sakamoto
    • Journal Title

      Angew. Chem. In. Ed.

      Volume: 52 Issue: 52 Pages: 13023-13025

    • DOI

      10.1002/anie.201205097

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Journal Article] Two-step Asymmetric Reaction Using the Frozen Chirality Generated by Spontaneous Crystallization2012

    • Author(s)
      Masami Sakamoto, et al
    • Journal Title

      Org. Lett

      Volume: 14 Issue: 10 Pages: 2638-2641

    • DOI

      10.1021/ol301033r

    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Peer Reviewed
  • [Presentation] クロモン誘導体の分子内光環化付加反応によるC2キラル大環状ポリエーテルの合成2014

    • Author(s)
      坂本昌巳,帷子哲,平良亮,吉田渉,八木下史敏,三野孝
    • Organizer
      2014日本化学会春期年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸エステルの光二量化反応による不斉発現2014

    • Author(s)
      馬場望美,八木下史敏,三野孝,坂本昌巳
    • Organizer
      2014日本化学会春期年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸誘導体の光二量化反応を利用したC2キラル配位子の開発2014

    • Author(s)
      上田祐揮,八木下史敏,三野孝,坂本昌巳
    • Organizer
      2014日本化学会春期年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 動的優先晶出法を用いたイソインドリノン誘導体の不斉合成2014

    • Author(s)
      石川紘輝,八木下史敏,三野孝,坂本昌巳
    • Organizer
      2014日本化学会春期年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] スクシンイミドの動的結晶化による不斉増幅2014

    • Author(s)
      坂本昌巳,國土由衣,八木下史敏,蜂屋祥子,笠嶋義夫,三野孝
    • Organizer
      2014日本化学会春期年会
    • Place of Presentation
      名古屋
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 動的結晶化を伴うアキラルな化合物からの不斉発現と増幅2013

    • Author(s)
      坂本昌巳,八木下史敏,蜂屋祥子,石川紘輝,馬場望美,三野孝
    • Organizer
      2013モレキュラーキラリティーシンポジウム
    • Place of Presentation
      京都
    • Year and Date
      2013-05-10
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 結晶化による軸不斉制御とキラルメモリー効果を利用した不斉合成法の開発2013

    • Author(s)
      八木下史敏, 高岸尚也, 三野孝, 桝飛雄真, 坂本昌巳
    • Organizer
      2013モレキュラーキラリティーシンポジウム
    • Place of Presentation
      京都
    • Year and Date
      2013-05-10
    • Related Report
      2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸エステルの光二量化による不斉発現2013

    • Author(s)
      坂本昌巳,馬場望美,八木下史敏,三野孝
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] アキラルなスクシンイミドの結晶化による不斉発現と増幅2013

    • Author(s)
      坂本昌巳,國土由衣,蜂屋祥子,八木下史敏,笠嶋義夫,三野孝
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸エステルの分子内光環化付加反応により生成するC2キラル大環状ポリエーテルの構造解析2013

    • Author(s)
      坂本昌巳,帷子哲,吉田渉,八木下史敏,三野孝
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 動的優先晶出を伴うアキラルな2-ベンゾイル安息香酸アミドからのイソインドリノンの不斉合成2013

    • Author(s)
      坂本昌巳,石川紘輝,八木下史敏,笠嶋義夫,三野孝
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Final Research Report
  • [Presentation] キラルな塩形成による芳香族アミド類の軸不斉制御と不斉合成への展開2013

    • Author(s)
      八木下史敏,高岸尚也,岡本一真,桝飛雄真,三野孝,坂本昌巳
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸誘導体の立体選択的光二量化反応2013

    • Author(s)
      坂本昌巳,馬場望美,八木下史敏,三野孝
    • Organizer
      2013年度光化学討論会
    • Place of Presentation
      松山
    • Related Report
      2013 Annual Research Report 2013 Final Research Report
  • [Presentation] クロモン誘導体の[2+2]光環化付加反応によるC2キラル大環状ポリエーテルの合成2013

    • Author(s)
      坂本昌巳,帷子哲,吉田渉,八木下史敏,三野孝
    • Organizer
      2013年度光化学討論会
    • Place of Presentation
      松山
    • Related Report
      2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸誘導体の[2 + 2]光環化付加反応による大環状ポリエーテルの合成2013

    • Author(s)
      坂本昌巳,吉田渉,帷子哲,三野孝
    • Organizer
      2013日本化学会春期年会
    • Place of Presentation
      大津
    • Related Report
      2013 Final Research Report
  • [Presentation] 2-クロモンカルボン酸エステルの光二量化による不斉発現2013

    • Author(s)
      坂本昌巳,馬場望美,八木下史敏,三野孝
    • Organizer
      2013日本化学会春期年会
    • Place of Presentation
      大津
    • Related Report
      2013 Final Research Report
  • [Presentation] クロモン誘導体の光二量化反応を利用したC2キラル配位子の開発2013

    • Author(s)
      坂本昌巳,上田祐揮,吉田渉,八木下史敏,三野孝
    • Organizer
      2013日本化学会春期年会
    • Place of Presentation
      大津
    • Related Report
      2013 Final Research Report
  • [Presentation] 動的優先晶出を伴うアキラルな 2-ベンゾイル安息香酸アミドからのイソインドリノンの不斉合成2013

    • Author(s)
      坂本昌巳, 石川紘輝, 八木下史敏 , 笠嶋義夫, 三野孝
    • Organizer
      2013年度有機結晶シンポジウム
    • Place of Presentation
      札幌
    • Related Report
      2013 Annual Research Report
  • [Presentation] クロモン誘導体の[2+2]光環化付加反応による C2キラル大環状ポリエーテルの合成2013

    • Author(s)
      坂本昌巳, 帷子哲, 吉田渉, 八木下史敏,三野孝
    • Organizer
      2013年度光化学討論会
    • Place of Presentation
      松山
    • Related Report
      2013 Annual Research Report
  • [Presentation] 結晶化による軸不斉制御とキラルメモリーを利用した不斉合成法の開発2013

    • Author(s)
      八木下史敏, 高岸尚也, 三野孝, 桝飛雄真, 坂本昌巳
    • Organizer
      2013モレキュラーキラリティーシンポジウム
    • Place of Presentation
      京都
    • Related Report
      2013 Annual Research Report
  • [Presentation] 2-クロモンカルボン酸誘導体の[2 + 2]光環化付加反応による大環状ポリエーテルの合成2013

    • Author(s)
      坂本 昌巳・吉田 渉・帷子 哲・三野 孝
    • Organizer
      2013春期年会
    • Place of Presentation
      大津
    • Related Report
      2012 Research-status Report
  • [Presentation] 2-クロモンカルボン酸エステルの光二量化による不斉発現2013

    • Author(s)
      坂本 昌巳・馬場 望美・八木下 史敏・三野 孝
    • Organizer
      2013春期年会
    • Place of Presentation
      大津
    • Related Report
      2012 Research-status Report
  • [Presentation] クロモン誘導体の光二量化反応を利用したC2キラル配位子の開発2013

    • Author(s)
      坂本 昌巳・上田 祐揮・吉田 渉・八木下 史敏・三野 孝
    • Organizer
      2013春期年会
    • Place of Presentation
      大津
    • Related Report
      2012 Research-status Report
  • [Presentation] Asymmetric Reaction Using Chiral Memory Derived from Chiral Salt Generated by Dynamic, Deracemization2012

    • Author(s)
      Masami Sakamoto
    • Organizer
      ICCEOCA-7/NICCEOCA-3/ACP2012
    • Place of Presentation
      Singapore
    • Related Report
      2013 Final Research Report
    • Invited
  • [Presentation] Photochemical Asymmetric Reaction Using Chiral Memory Derived from Chiral Salts Generated by Dynamic Deracemization2012

    • Author(s)
      Masami Sakamoto
    • Organizer
      IPC 2012
    • Place of Presentation
      大阪
    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Invited
  • [Presentation] クロモン誘導体の[2 + 2]光環化付加反応による大環状ポリエーテルの合成2012

    • Author(s)
      吉田渉, 三野孝, 坂本昌巳
    • Organizer
      2012年度光化学討論会
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report
  • [Presentation] 優先晶出を伴う2-クロモンカルボン酸エステルのエナンチオ選択的光二量化反応2012

    • Author(s)
      八木下史敏, 馬場望美, 三野孝, 坂本昌巳
    • Organizer
      2012年度光化学討論会
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report
  • [Presentation] ラセミ化優先晶出法によるラセミ体環状イミドの完全分割2012

    • Author(s)
      坂本昌巳,蜂屋祥子,八木下史敏,大貫達夫・三野孝
    • Organizer
      有機結晶シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] 2-クロモンカルボン酸エステルの光二量化反応における不斉発現2012

    • Author(s)
      坂本昌巳, 馬場望美, 八木下史敏, 三野孝
    • Organizer
      有機結晶シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] ラセミ化優先晶出法を用いたイソインドリノン誘導体の完全分割2012

    • Author(s)
      坂本昌巳, 石川紘輝, 八木下史敏, 蜂屋祥子, 三野孝
    • Organizer
      有機結晶シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] 結晶化による不斉情報の記録と不斉反応への展開2012

    • Author(s)
      坂本昌巳
    • Organizer
      有機結晶シンポジウム
    • Place of Presentation
      東京
    • Related Report
      2013 Final Research Report 2012 Research-status Report
    • Invited
  • [Presentation] Chiral Induction Using Preferential Crystallization Involving Photoracemization2012

    • Author(s)
      Masami Sakamoto, Fumitoshi Yagishita, Naoya Takagishi, Takashi Mino
    • Organizer
      MCASIA 2012
    • Place of Presentation
      福岡
    • Related Report
      2013 Final Research Report 2012 Research-status Report
  • [Presentation] クロモン誘導体の[2 + 2]光環化付加反応による大環状ポリエーテルの合成2012

    • Author(s)
      吉田渉・三野孝・坂本昌巳
    • Organizer
      光化学討論会
    • Place of Presentation
      東京
    • Related Report
      2012 Research-status Report
  • [Presentation] 優先晶出を伴う2-クロモンカルボン酸エステルのエナンチオ選択的光二量化反応2012

    • Author(s)
      八木下史敏・馬場望美・三野孝・坂本昌巳
    • Organizer
      光化学討論会
    • Place of Presentation
      東京
    • Related Report
      2012 Research-status Report
  • [Presentation] Asymmetric Reaction Using Chiral Memory Derived from Chiral Salt Generated by Dynamic Deracemization2012

    • Author(s)
      Masami Sakamoto
    • Organizer
      ICCEOCA-7/NICCEOCA-3/ACP2012
    • Place of Presentation
      Singapore
    • Related Report
      2012 Research-status Report
    • Invited
  • [Remarks] 研究室ホームページ

    • URL

      http://chem.tf.chiba-u.jp/gacb06/index.html

    • Related Report
      2013 Annual Research Report

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Published: 2013-05-31   Modified: 2019-07-29  

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