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Control of handedness in absolute asymmetric synthesis

Research Project

Project/Area Number 17K19114
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Research Field Organic chemistry and related fields
Research InstitutionChiba University

Principal Investigator

Sakamoto Masami  千葉大学, 大学院工学研究院, 教授 (00178576)

Project Period (FY) 2017-06-30 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Fiscal Year 2018: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Fiscal Year 2017: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Keywordsキラル光 / 絶対不斉合成 / 不斉制御 / 結晶核 / 結晶成長 / 有機化学 / 結晶工学 / ホモキラリティー / 不斉発現 / キラル渦光
Outline of Final Research Achievements

The development of a new methodology for creating optically pure compounds from prochiral precursors has been focused in many research fields in relation to high homogeneity expression in nature. In this study, we developed an chirality control method using the unique phenomenon that the chirality naturally expresses when the organic compound crystallizes. Specifically, chirality of crystal nucleation and crystal growth were controlled by irradiating a supersaturated solution of prochiral compound with chiral vortex laser light. We succeeded in transfer and conversion of physical chirality to chemical molecular chirality.

Academic Significance and Societal Importance of the Research Achievements

新しい不斉制御法の開発は,キラル材料やキラル創薬分野で強く求められている。また,自然界の高度なホモキラリティー発現は多くの研究領域で注目されている課題である。本研究では,プロキラルな化合物の結晶化をキラル渦レーザー光を用いて制御し,不斉発現と不斉増幅の協働による絶対不斉合成へと展開する前例のない成果であり,不斉有機合成分野のブレークスルーとなる。さらに,有機化学者ばかりでなく異分野の多くの研究者に大きなインパクトを与え,新たな研究領域の創生に繋がる可能性がある。

Report

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

    (45 results)

All 2018 2017 Other

All Journal Article (16 results) (of which Peer Reviewed: 16 results,  Acknowledgement Compliant: 2 results) Presentation (28 results) (of which Int'l Joint Research: 5 results,  Invited: 2 results) Remarks (1 results)

  • [Journal Article] Stereoselective Photodimerization of 3-Arylindenones in Solution and in the Solid-State2018

    • Author(s)
      Naohiro Uemura, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 4 Pages: 624-631

    • DOI

      10.1021/acs.joc.7b03147

    • Related Report
      2018 Annual Research Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] A Facile Synthesis of C2-Symmetric Macrocyclic Polyethers by Photodimerization of Covalently-linked Flavonoid Derivatives2018

    • Author(s)
      Naohiro Uemura, Hiroki Ishikawa, Wataru Yoshida, Satoshi Katabira, Fumitoshi Yagishita, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima and Masami Sakamoto
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 2 Pages: 160-162

    • DOI

      10.1246/cl.170955

    • NAID

      130006337720

    • Related Report
      2018 Annual Research Report 2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Diels-Alder Reaction Involving Dynamic Enantioselective Crystallization2018

    • Author(s)
      Naohiro Uemura, Seiya Toyoda, Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 16 Pages: 9300-9304

    • DOI

      10.1021/acs.joc.8b01273

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Umpolung Cyclization Reaction of N-Cinnamoylthioureas in the Presence of DBU2018

    • Author(s)
      Rei Saito, Naohiro Uemura, Hiroki Ishikawa, Akina Magara, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, and Masami Sakamoto
    • Journal Title

      Org. Biomol. Chem.

      Volume: 16 Issue: 42 Pages: 7910-7919

    • DOI

      10.1039/c8ob02066c

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The second-generation synthesis of BICMAP analogues2018

    • Author(s)
      Mino Takashi、Watanabe Kohei、Akiyama Takumu、Mizutani Yuki、Miura Kazuki、Hashimoto Masatoshi、Yoshida Yasushi、Sakamoto Masami
    • Journal Title

      Tetrahedron

      Volume: 74 Issue: 28 Pages: 3871-3878

    • DOI

      10.1016/j.tet.2018.05.062

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Regio- and Enantioselective Synthesis of α-Amino-δ-Ketoesters Through Catalytic Umpolung Reaction of α-Iminoesters with Enones2018

    • Author(s)
      Yasushi Yoshida, Yuta Moriya, Takashi Mino, Masami Sakamoto
    • Journal Title

      Adv. Synth. Catal.

      Volume: 360 Pages: 4142-4146

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 立体選択的な動的結晶化を利用した不斉反応の開発2018

    • Author(s)
      上村直弘,石川紘輝,坂本昌巳
    • Journal Title

      化学工業、Chemical Industry

      Volume: 69 Pages: 37-45

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrazone-Pd-catalyzed direct intermolecular reaction of o-alkynylphenols with allylic acetate2018

    • Author(s)
      Kohei Watanabe, Takashi Mino, Eri Ishikawa, Chihiro Masuda, Yasushi Yoshida, Masami Sakamoto
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 16 Issue: 4 Pages: 575-584

    • DOI

      10.1039/c7ob02873c

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis by Using Natural Sunlight under Absolute Achiral Conditions2017

    • Author(s)
      Masami Sakamoto, Koh Shiratsuki, Naohiro Uemura, Hiroki Ishikawa, Yasushi Yoshida, Yoshio Kasashima, and Takashi Mino
    • Journal Title

      Chemistry A European Journal

      Volume: 23 Issue: 7 Pages: 1310-1312

    • DOI

      10.1002/chem.201605583

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of o-Allyloxyethynylbenzene Derivatives via Cu-Catalyzed Suzuki-Miyaura-Type Reaction and Their Transformations for Heterocyclic Compounds2017

    • Author(s)
      Kohei Watanabe, Takashi Mino, Eri Ishikawa, Miyu Okano, Tatsuya Ikematsu, asushi Yoshida, Masami Sakamoto,Kazuki Sato and Kazuhiro Yoshida
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2017 Issue: 16 Pages: 2359-2368

    • DOI

      10.1002/ejoc.201700217

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Asymmetric Synthesis Using Crystal Chirality2017

    • Author(s)
      Masami Sakamoto, Takashi Mino, Yasushi Yoshida
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 75 Issue: 5 Pages: 509-521

    • DOI

      10.5059/yukigoseikyokaishi.75.509

    • NAID

      130006903199

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Hydrazone-catalyzed Suzuki-Miyaura-type reactions of dibromoalkenes with arylboronic acids2017

    • Author(s)
      Kohei Watanabe, Takashi Mino, Chikako Hatta, Eri Ishikawa, Yasushi Yoshida, Masami Sakamoto
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2017 Issue: 25 Pages: 3612-3619

    • DOI

      10.1002/ejoc.201700535

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Organocatalytic Highly Regio- and Enantioselective Umpolung Michael Addition Reaction of α- Imino Esters2017

    • Author(s)
      Yasushi Yoshida, Takashi Mino, Masami Sakamoto
    • Journal Title

      Chemistry - A European Journal

      Volume: 23 Issue: 52 Pages: 12749-12753

    • DOI

      10.1002/chem.201703479

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Mizoroki-Heck Reaction of Aryl Iodides with Allyl Aryl Ethers Using Imidazo[1, 5-a] pyridines2017

    • Author(s)
      Fumitoshi Yagishita, Sota Shimokawa, Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Masami Sakamoto, and Yasuhiko Kawamura
    • Journal Title

      ChemistrySelect

      Volume: 2 Issue: 31 Pages: 10143-10145

    • DOI

      10.1002/slct.201702337

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Dimeric Imidazo[1, 5-a]pyridines and Their Photophysical Properties2017

    • Author(s)
      Fumitoshi Yagishita, Natsumi Kozai, Chiho Nii, Yoshihiko Tezuka, Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Masami Sakamoto, and Yasuhiko Kawamura
    • Journal Title

      ChemistrySelect

      Volume: 2 Issue: 33 Pages: 10143-10145

    • DOI

      10.1002/slct.201702277

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis Involving Reversible Photodimerization of a Prochiral Flavonoid Followed by Crystallization2017

    • Author(s)
      Hiroki Ishikawa, Naohiro Uemura, Fumitoshi Yagishita, Nozomi Baba, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, and Masami Sakamoto
    • Journal Title

      Eur. J. Org. Chem.

      Volume: 2017 Issue: 46 Pages: 6878-6881

    • DOI

      10.1002/ejoc.201701457

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] 動的晶出過程を経る不斉Diels-Alder反応2018

    • Author(s)
      豊田 聖耶, 上村 直弘, 吉田 泰志, 三野 孝, 笠嶋 義夫, 坂本 昌巳
    • Organizer
      シンポジウムモレキュラーキラリティー2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 共役付加反応および動的結晶化によるα-アミノ酸誘導体の絶対不斉合成2018

    • Author(s)
      上村 直弘, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      シンポジウムモレキュラーキラリティー2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] 光渦レーザー照射によるエナンチオ選択的結晶成長2018

    • Author(s)
      斎藤 玲, 上村 直弘, 石川 紘輝, 吉田 泰志, 三野 孝, 尾松 孝茂, 坂本 昌巳
    • Organizer
      シンポジウムモレキュラーキラリティー2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] Michael付加反応および動的晶出法によるアミノ酸誘導体の絶対不斉合成2018

    • Author(s)
      上村 直弘, 佐野 健人, 吉田 泰志, 三野 孝, 坂本 昌巳
    • 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] Asymmetric Synthesis Using Crystal Chirality2018

    • Author(s)
      Masami Sakamoto
    • Organizer
      MCASIA2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Transformation of Succinimides via Stereoselective Dynamic Crystallization2018

    • Author(s)
      Hiroki Ishikawa, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
    • Organizer
      MCASIA2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Absolute Asymmetric Synthesis of Amino Acid Derivative Involving Dynamic Crystallization2018

    • Author(s)
      Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
    • Organizer
      MCASIA2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric Photochemical reaction involving dynamic crystallization2018

    • Author(s)
      Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Yoshio Kasashima, Masami Sakamoto
    • Organizer
      光化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的晶出過程を経るフラバノンの絶対不斉合成2018

    • Author(s)
      清水 和久, 上村 直弘, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      2019日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 絶対不斉Diels-Alder反応の開発2018

    • Author(s)
      豊田 聖耶, 上村 直弘, 石川 紘輝, 吉田 泰志, 三野 孝, 笠嶋 義夫, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的晶出法による光学活性スピロピラン類の創成2018

    • Author(s)
      斎藤 玲, 上村 直弘, 石川 紘輝, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的結晶化を利用したメソジオール類の非対称化による不斉増幅2018

    • Author(s)
      鷲尾 葵, 上村 直弘, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的晶出法を用いたアミノ酸誘導体の絶対不斉合成2018

    • Author(s)
      上村 直弘, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] チオヒダントイン誘導体の動的晶出法による完全光学分割2018

    • Author(s)
      穂坂 桃香, 上村 直弘, 吉田 泰志, 三野 孝, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] キラル渦レーザー光照射による結晶成長のキラリティー制御2018

    • Author(s)
      斎藤 玲, 上村 直弘, 石川 紘輝, 吉田 泰志, 三野 孝, 尾松 孝茂, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的晶出法によるニコチンアミド誘導体の軸不斉制御2018

    • Author(s)
      坂 一真, 石川 紘輝, 吉田 泰志, 笠嶋 義夫, 三野 孝, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Diels-Alder反応と動的晶出法による不斉の発現と増幅2018

    • Author(s)
      豊田 聖耶, 上村 直弘, 石川 紘輝, 吉田 泰志, 三野 孝, 笠嶋 義夫, 坂本 昌巳
    • Organizer
      2019年日本化学会春期年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] アルキリデンオキサゾロンの立体選択的光二量化反応2018

    • Author(s)
      石川 紘輝・坂 一真・上村 直弘・吉田 泰志・笠嶋 義夫・三野 孝・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 光渦レーザー照射による結晶成長のキラリティー制御2018

    • Author(s)
      上村 直弘・斎藤 玲・石川 紘輝・吉田 泰志・三野 孝・尾松 孝茂・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] エナンチオ選択的動的晶出過程を経るフラボン類の絶対不斉合成2018

    • Author(s)
      上村 直弘・清水 和久・吉田 泰志・三野 孝・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 可逆的Di el s-Al der反応と動的晶出法による絶対不斉合成2018

    • Author(s)
      上村 直弘・豊田 聖耶・吉田 泰志・三野 孝・笠嶋 義夫・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Mi chael 付加反応および動的晶出法によるアスパラギン酸誘導体の絶対不斉合成2018

    • Author(s)
      上村 直弘・吉田 泰志・三野 孝・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] スクシンイミドの立体選択的動的結晶化による完全光学分割2018

    • Author(s)
      石川 紘輝・桝 飛雄真・吉田 泰志・三野 孝・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 動的結晶化によるスピロピラン類の不斉制御2018

    • Author(s)
      斎藤 玲・上村 直弘・吉田 泰志・三野 孝・坂本 昌巳
    • Organizer
      日本化学会第98春期年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Asymmetric Synthesis using Crystal Chirality2017

    • Author(s)
      Masami Sakamoto
    • Organizer
      Chiraliy2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Total resolution of Thiohydantoin Der vatives by Dynamic Crystallization2017

    • Author(s)
      Naohiro Uemura, Yasushi Yoshida, Takashi Mino, Masami Sakamoto
    • Organizer
      Chiraliy2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] キラル光を用いた結晶化におけるキラリティー制御の試み2017

    • Author(s)
      上村 直弘・斎藤 玲・尾松 孝茂・吉田 泰志・三野 孝・坂本 昌巳
    • Organizer
      2017年有機結晶シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] 動的晶出を伴う不斉Diels-Alder反応の開発2017

    • Author(s)
      上村直弘,豊田聖耶,石川紘輝,吉田泰志,三野孝,笠嶋義夫,坂本昌巳
    • Organizer
      2017年有機結晶シンポジウム
    • Related Report
      2017 Research-status Report
  • [Remarks]

    • URL

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

    • Related Report
      2018 Annual Research Report

URL: 

Published: 2017-07-21   Modified: 2020-03-30  

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