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Asymmetric Synthesis and Function Development of Silicon-Stereogenic Novel pi-Conjugated Compounds

Research Project

Project/Area Number 16H04145
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka University

Principal Investigator

SHINTANI Ryo  大阪大学, 基礎工学研究科, 教授 (50372561)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥18,070,000 (Direct Cost: ¥13,900,000、Indirect Cost: ¥4,170,000)
Fiscal Year 2018: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2017: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2016: ¥8,710,000 (Direct Cost: ¥6,700,000、Indirect Cost: ¥2,010,000)
Keywords不斉ケイ素中心 / π共役化合物 / 触媒的不斉合成 / ケイ素不斉 / 反応機構解析 / 有機ケイ素化合物 / 不斉合成
Outline of Final Research Achievements

Optically active compounds are widely used in various fields including medicines, pesticides, and organic materials, but asymmetric synthesis of silicon-stereogenic organosilanes had not been well investigated. In this research, we focused on the development of catalytic asymmetric synthesis of silicon-stereogenic silicon-bridged pi-conjugated compounds and examination of the properties of resulting compounds in the hope of expression of chiroptical properties. As a result, we could achieve the synthesis of various silicon-bridged pi-conjugated compounds such as dibenzosilole derivatives that were difficult to synthesize using existing methods. We could also succeed in obtaining those compounds with high enantioselectivity in many cases. In addition, we could acquire important information on the mechanisms of the reactions we developed as well as optical properties of the compounds we synthesized.

Academic Significance and Societal Importance of the Research Achievements

本研究は、これまであまり研究がなされてこなかった不斉ケイ素中心を持つ化合物の不斉合成のなかでも、分子の機能開拓を念頭に置いてケイ素架橋π共役化合物を主なターゲットとした反応開発および物性評価に関するものであり、学術的新規性は非常に高いと考えられる。研究の性質上、その成果がすぐさま社会に還元されるわけではないが、本研究によって、新たな分子変換反応の開発を通じて様々な不斉ケイ素中心を持つ新しい有機ケイ素化合物の不斉合成が可能になるとともに、得られた化合物の物性評価においても一定の成果を挙げることができ、有機合成化学ばかりでなく、有機金属化学や材料化学など関連諸分野への貢献は大きいと言える。

Report

(4 results)
  • 2019 Final Research Report ( PDF )
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (41 results)

All 2020 2019 2018 2017 2016

All Journal Article (11 results) (of which Peer Reviewed: 11 results,  Acknowledgement Compliant: 3 results,  Open Access: 1 results) Presentation (30 results) (of which Int'l Joint Research: 8 results,  Invited: 6 results)

  • [Journal Article] Synthesis of 7H-Benzo[e]naphtho[1,8-bc]silines by Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition2020

    • Author(s)
      Maesato, T.; Shintani, R.
    • Journal Title

      Chem. Lett.

      Volume: 49 Issue: 4 Pages: 344-346

    • DOI

      10.1246/cl.200025

    • NAID

      130007828846

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Synthesis of Benzophenanthrosilines by C-H/C-H Coupling through 1,4-Palladium Migration/Alkene Stereoisomerization2020

    • Author(s)
      Tsuda, T.; Kawakami, Y.; Choi, S.-M.; Shintani, R.
    • Journal Title

      Angew. Chem., Int. Ed.

      Volume: 59 Issue: 21 Pages: 8057-8061

    • DOI

      10.1002/anie.202000217

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium-Catalyzed Synthesis of Silicon-Bridged 1,2-Dialkenylbenzenes via 1,4-Rhodium Migration2019

    • Author(s)
      Miwa, T.; Shintani, R.
    • Journal Title

      Org. Lett.

      Volume: 21 Issue: 6 Pages: 1627-1631

    • DOI

      10.1021/acs.orglett.9b00167

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Intramolecular C-H Arylation vs. 1,5-Palladium Migration: Theoretical Investigation2018

    • Author(s)
      Misawa, N.; Tsuda, T.; Shintani, R.; Yamashita, K.; Nozaki, K.
    • Journal Title

      Chem. Asian J.

      Volume: 13 Issue: 17 Pages: 2566-2572

    • DOI

      10.1002/asia.201800603

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Recent Progress in Catalytic Enantioselective Desymmetrization of Prochiral Organosilanes for the Synthesis of Silicon-Stereogenic Compounds2018

    • Author(s)
      Shintani Ryo
    • Journal Title

      Synlett

      Volume: 29 Issue: 04 Pages: 388-396

    • DOI

      10.1055/s-0036-1591839

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Structures and Physical Properties of Chemically Reduced Diindenosiloles and Their π-Extended Derivatives2017

    • Author(s)
      Takano Ryo、Shintani Ryo、Fukazawa Aiko、Yamaguchi Shigehiro、Nakabayashi Koji、Ohkoshi Shin-ichi、Nozaki Kyoko
    • Journal Title

      Organometallics

      Volume: 36 Issue: 14 Pages: 2646-2653

    • DOI

      10.1021/acs.organomet.7b00260

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration2017

    • Author(s)
      Sato Yosuke、Takagi Chihiro、Shintani Ryo、Nozaki Kyoko
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 31 Pages: 9211-9216

    • DOI

      10.1002/anie.201705500

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Selective Synthesis of Unsymmetric Dibenzo[a,e]pentalenes by Rhodium-Catalysed Stitching Reaction2017

    • Author(s)
      K. Takahashi, S. Ito, R. Shintani, K. Nozaki
    • Journal Title

      Chemical Science

      Volume: 8 Issue: 1 Pages: 101-107

    • DOI

      10.1039/c6sc04560j

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Rhodium-Catalyzed Synthesis and Optical Properties of Silicon-Bridged Arylpyridines2017

    • Author(s)
      Ryo Shintani, Nana Misawa, Ryo Takano, Kyoko Nozaki
    • Journal Title

      Chem. Eur. J.

      Volume: 23 Issue: 11 Pages: 2660-2665

    • DOI

      10.1002/chem.201605000

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Quinoidal Fused Oligosiloles by Rhodium-Catalyzed Stitching Reaction and Theoretical Investigation of Their Properties2017

    • Author(s)
      Ryo Shintani, Nana Misawa, Tomohiro Tsuda, Ryo Iino, Mikiya Fujii, Koichi Yamashita, Kyoko Nozaki
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 139 Issue: 10 Pages: 3861-3867

    • DOI

      10.1021/jacs.7b00344

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Intermolecular Three-Component Arylsilylation of Alkynes under Palladium/Copper Cooperative Catalysis2016

    • Author(s)
      Ryo Shintani, Hiroki Kurata, Kyoko Nozaki
    • Journal Title

      J. Org. Chem.

      Volume: 81 Issue: 8 Pages: 3065-3069

    • DOI

      10.1021/acs.joc.6b00587

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 拡張π共役化合物合成のための反応開発2020

    • Author(s)
      新谷 亮
    • Organizer
      近畿化学協会有機金属部会2019年度第4回例会
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] [2+2+2]付加環化反応によるベンゾナフトシリンの触媒的合成2020

    • Author(s)
      前里拓実、新谷 亮
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Selective Synthesis of Benzophenanthrosilines through a New 1,4-Palladium Migration2020

    • Author(s)
      津田知拓、川上由夏、チェスンミン、新谷 亮
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] C-H/C-Hカップリングを経由するパラジウム触媒を用いたベンゾフェナントロシリンの合成2019

    • Author(s)
      津田知拓、川上由夏、崔 承旻、新谷 亮
    • Organizer
      第52回有機金属若手の会夏の学校
    • Related Report
      2018 Annual Research Report
  • [Presentation] Selective Synthesis of Benzonaphthosilines by Rhodium-Catalyzed [2 + 2 + 2] Cycloaddition2019

    • Author(s)
      Takumi Maesato, Ryo Shintani
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Selective Synthesis of 8H-Benzo[e]phenanthro[1,10-bc]silines under Palladium Catalysis2019

    • Author(s)
      Tomohiro Tsuda, Yuka Kawakami, Seung-Min Choi, Ryo Shintani
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] C-H/C-Hカップリングを経由するパラジウム触媒を用いたベンゾフェナントロシリンの合成2019

    • Author(s)
      津田知拓、川上由夏、チェスンミン、新谷 亮
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ロジウム触媒を用いた[2+2+2]付加環化反応によるベンゾナフトシリンの選択的合成2019

    • Author(s)
      前里拓実、新谷 亮
    • Organizer
      第36回有機合成化学セミナー
    • Related Report
      2018 Annual Research Report
  • [Presentation] パラジウム触媒を用いたケイ素架橋π共役化合物の合成2019

    • Author(s)
      新谷 亮
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Catalytic Asymmetric Synthesis of Silicon-Stereogenic N-Heterocycles via Enantioselective 1,5-Palladium Migration2018

    • Author(s)
      Ryo Shintani
    • Organizer
      4th International Conference on Organometallic and Catalysis 2018
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ロジウムの1,4-転位を利用した新規ケイ素架橋π共役化合物の触媒的合成2018

    • Author(s)
      三輪琢哉、新谷 亮
    • Organizer
      第38回有機合成若手セミナー
    • Related Report
      2018 Annual Research Report
  • [Presentation] Catalytic Asymmetric Synthesis of Silicon-Stereogenic Dibenzosiloles and Related Compounds2018

    • Author(s)
      Ryo Shintani
    • Organizer
      6th Japan-UK Symposium on Asymmetric Catalysis
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ロジウム触媒を用いた1,5-ジイン類の縫合型重合反応による新規π共役高分子化合物の合成2018

    • Author(s)
      池田 翔、新谷 亮
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ロジウムの1,4-転位を利用した新規ケイ素架橋π共役化合物の触媒的合成2018

    • Author(s)
      三輪 琢哉、新谷 亮
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis of Quinoidal Fused Oligosiloles by Rhodium-Catalyzed Stitching Reaction and Investigation of Their Properties2017

    • Author(s)
      Shintani Ryo
    • Organizer
      Spanish-Japanese Symposium on Modern Synthetic Methodology
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ロジウム触媒を用いた縫合反応によるキノイド型縮環オリゴシロールの合成および物性2017

    • Author(s)
      新谷 亮
    • Organizer
      第37回有機合成若手セミナー
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration2017

    • Author(s)
      Sato Yosuke、Takagi Chihiro、Shintani Ryo、Nozaki Kyoko
    • Organizer
      19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Catalytic Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration2017

    • Author(s)
      Shintani Ryo、Sato Yosuke、Takagi Chihiro、Nozaki Kyoko
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis of Quinoidal Fused Oligosiloles by Rhodium-Catalyzed Stitching Reaction and Theoretical Investigation of Their Properties2017

    • Author(s)
      Tsuda Tomohiro、Shintani Ryo、Misawa Nana、Iino Ryo、Fujii Mikiya、Yamashita Koichi、Nozaki Kyoko
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 縫合反応によるキノイド型縮環オリゴシロールの合成および物性探索2017

    • Author(s)
      津田 知拓、新谷 亮、野崎 京子
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] Palladium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic 5,10-Dihydrophenazasilines via Enantioselective 1,5-Palladium Migration2017

    • Author(s)
      佐藤 陽介、高木 智博、新谷 亮、野崎 京子
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] キノイド型縮環オリゴシロールの化学還元およびその構造と物性2017

    • Author(s)
      高野 遼、新谷 亮、深澤 愛子、山口 茂弘、中林 耕二、大越 慎一、野崎 京子
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] ロジウム触媒を用いた縫合反応による新規キノイド型縮環オリゴシロールの合成および物性2016

    • Author(s)
      新谷 亮、飯野 亮、津田 知拓、野崎 京子
    • Organizer
      第109回有機合成シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] Rhodium-Catalyzed Stitching Reaction Leading to Unsyammetriac Dibenzo[a,e]Pentalenes2016

    • Author(s)
      Takahashi Keisuke、Ito Shingo、Shintani Ryo、Nozaki Kyoko
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rhodium-Catalyzed Asymmetric Synthesis of Silicon-Stereogenic Silicon-Bridged Arylpyridinones2016

    • Author(s)
      Takano Ryo、Shintani Ryo、Nozaki Kyoko
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ロジウム触媒を用いた縫合反応による非対称ジベンゾ[a,e]ペンタレン誘導体の合成と物性評価2016

    • Author(s)
      高橋 京佑、伊藤 慎庫、新谷 亮、野崎 京子
    • Organizer
      第27回基礎有機化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] キノイド型縮環オリゴシロールの還元2016

    • Author(s)
      高野 遼、飯野 亮、新谷 亮、深澤 愛子、山口 茂弘、野崎 京子
    • Organizer
      第27回基礎有機化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] 新規ケイ素架橋アリールピリジンのロジウム触媒による選択的合成と光学特性2016

    • Author(s)
      三澤 奈々、高野 遼、新谷 亮、野崎 京子
    • Organizer
      第63回有機金属化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] ロジウム触媒によるケイ素不斉中心を持つケイ素架橋アリールピリジノンの不斉合成2016

    • Author(s)
      高野 遼、新谷 亮、野崎 京子
    • Organizer
      第6回CSJ化学フェスタ2016
    • Related Report
      2016 Annual Research Report
  • [Presentation] ロジウム触媒を用いた縫合反応による非対称ジベンゾ[a,e]ペンタレン誘導体の合成2016

    • Author(s)
      高橋 京佑、伊藤 慎庫、新谷 亮、野崎 京子
    • Organizer
      第6回CSJ化学フェスタ2016
    • Related Report
      2016 Annual Research Report

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Published: 2016-04-21   Modified: 2021-02-19  

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