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Development of unique pai-conjugated smart materials based on the catalytic and regioselective functionalization of azulenes

Research Project

Project/Area Number 16K05778
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionOkayama University

Principal Investigator

Murai Masahito  岡山大学, 自然科学研究科, 助教 (40647070)

Project Period (FY) 2016-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000)
Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2017: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2016: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywordsアズレン / 多環芳香族炭化水素 / 双極子 / フェナセン / アリール化 / 移動度 / 脱酸素芳香族化 / アライン / HOMO-LUMOギャップ / 有機電界効果トランジスタ / アセン / 直截アリール化 / パラジウム / 炭素-水素結合活性化 / π共役系分子 / C-H結合官能基化 / 機能性分子材料
Outline of Final Research Achievements

Uniquely polarized hydrocarbon, azulene, possesses unusual photophysical and electrochemical properties that are unique for small molecules without any hetero atoms. The main purpose of the present study is development of a regioselective functionalization methods to further extend and disclose its potential new functions. As a result of investigation, (1) regioselective direct arylation of the carbon-hydrogen bond of azulene, (2) method for incorporation of azulene rings into phenacene and acene skeletons, and (3) regioselective arene homologation through deoxygenative aromatization were developed, and the performance of the resulting products as components for organic field-effect transistors was evaluated.

Academic Significance and Societal Importance of the Research Achievements

本研究で得られた縮環芳香族炭化水素は、アズレン骨格に由来した狭いHOMO-LUMOギャップを有し、凝集状態において、双極子に沿ってその会合構造を制御可能な新規分子デバイス素子として期待できる。本研究で確立したアズレンの効率的な官能基化法を駆使することで、様々な新しい類縁体の物性を明らかにでき、電子材料を設計する上での新たな指針を得ることができた。

Report

(5 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (40 results)

All 2019 2018 2017 2016

All Journal Article (15 results) (of which Peer Reviewed: 15 results,  Open Access: 3 results,  Acknowledgement Compliant: 1 results) Presentation (24 results) (of which Int'l Joint Research: 6 results,  Invited: 6 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Regioselective Functionalization of 9,9-Dimethyl-9-silafluorenes by Borylation, Bromination, and Nitration2019

    • Author(s)
      Masahito Murai, Naoki Nishinaka, Mizuki Kimura, Kazuhiko Takai
    • Journal Title

      Journal of. Organic Chemistry

      Volume: 84 Issue: 9 Pages: 5667-5676

    • DOI

      10.1021/acs.joc.9b00598

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Unsymmetrical Difunctionalization of Two Different C-H Bonds in One-Pot Under Transition Metal Catalysis2019

    • Author(s)
      Masahito Murai, Kazuhiko Takai
    • Journal Title

      Synthesis

      Volume: 51 Issue: 01 Pages: 40-54

    • DOI

      10.1055/s-0037-1611066

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Regioselective Arene Homologation through Rhenium-Catalyzed Deoxygenative Aromatization of 7-Oxabicyclo[2.2.1]hepta-2,5-diene2019

    • Author(s)
      Masahito Murai, Takuya Ogita, Kazuhiko Takai
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 16 Pages: 2332-2335

    • DOI

      10.1039/c9cc00270g

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Double-Bond Migration of Unsaturated Hydrocarbons Controllable by Second Metal Catalysts2019

    • Author(s)
      Masahito Murai, Kengo Nishimura, Kazuhiko Takai
    • Journal Title

      Chemical Communications

      Volume: 55 Issue: 19 Pages: 2769-2772

    • DOI

      10.1039/c9cc00223e

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on the Regioselective C-H Bond Activation2018

    • Author(s)
      Masahito Murai, Naoki Nishinaka, Kazuhiko Takai
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 20 Pages: 5843-5847

    • DOI

      10.1002/anie.201801229

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Amine-Promoted anti-Markovnikov Addition Reaction of 1,3-Dicarbonyl Compounds with Terminal Alkynes under Rhenium Catalysis2018

    • Author(s)
      Masahito Murai, Erika Uemura, Kazuhiko Takai
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 6 Pages: 5454-5459

    • DOI

      10.1021/acscatal.8b01338

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Catalytic Cleavage and Reformation of Ethereal sigma-Bonds2018

    • Author(s)
      Masahito Murai, Kazuki Origuchi, Kazuhiko Takai
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 7 Pages: 927-930

    • DOI

      10.1246/cl.180361

    • NAID

      130007402758

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Dehydrogenative Dimerization of Benzylmethylsilanes via Silylation of C(sp3)-H Bonds Adjacent to a Silicon Atom2017

    • Author(s)
      Masahito Murai, Yutaro Takeuchi, Kazuhiko Takai
    • Journal Title

      Chemistry Letters

      Volume: 46 Issue: 7 Pages: 1044-1047

    • DOI

      10.1246/cl.170369

    • NAID

      130005709528

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Iridium-Catalyzed Hydrosilylation of Cyclopropanes via Regioselective Carbon-Carbon Bonds Cleavage2017

    • Author(s)
      Masahito Murai, Atsushi Nishiyama, Naoki Nishinaka, Haruka Morita, Kazuhiko Takai
    • Journal Title

      Chemical Communications

      Volume: 53 Issue: 66 Pages: 9281-9284

    • DOI

      10.1039/c7cc04296e

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Structural Characterization and Unique Catalytic Performance of Reactive Silyl-Substituted Geminal Dichromiomethane Complexes Stabilized with Diamine Ligand2017

    • Author(s)
      Masahito Murai, Ryuji Taniguchi, Naoki Hosokawa, Yusuke Nishida, Hiroko Mimachi, Toshiyuki Oshiki, Kazuhiko Takai
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 37 Pages: 13184-13192

    • DOI

      10.1021/jacs.7b07487

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Azulene-Fused Linear-Shaped Polycyclic Aromatic Hydrocarbons with Low Bandgap and Unique Stimuli-Responsiveness2017

    • Author(s)
      Masahito Murai, Shinji Iba, Hiromi Ota, Kazuhiko Takai
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 20 Pages: 5585-5588

    • DOI

      10.1021/acs.orglett.7b02729

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Straightforward Approach to Borylcyclopropanes by Chromium-Promoted Cyclopropanation of Unactivated Alkenes2017

    • Author(s)
      Masahito Murai, Chisato Mizuta, Ryuji Taniguchi, and Kazuhiko Takai
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 22 Pages: 6104-6107

    • DOI

      10.1021/acs.orglett.7b02956

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Rhenium-Catalyzed ortho-Alkylation of Phenols2017

    • Author(s)
      Yoichiro Kuninobu, Masaki Yamamoto, Mitsumi Nishi, Tomoyuki Yamamoto, Takashi Matsuki, Masahito Murai, Kazuhiko Takai
    • Journal Title

      Organic Syntheses

      Volume: 94 Pages: 280-291

    • DOI

      10.15227/orgsyn.094.0280

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Rhenium-Catalyzed Construction of Polycyclic Hydrocarbon Frameworks by Unique Cyclization of 1,n-Diynes Initiated by 1,1-Difunctionalization with Carbon Nucleophiles2017

    • Author(s)
      Murai, Masahito; Uemura, Erika; Hori, Shunsuke; Takai, Kazuhiko
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 56 Issue: 21 Pages: 5862-5866

    • DOI

      10.1002/anie.201701159

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Sila[n]helicenes via Dehydrogenative Silylation of C-H Bonds under Rhodium Catalysis2016

    • Author(s)
      Masahito Murai, Ryo Okada, Atsushi Nishiyama, Kazuhiko Takai
    • Journal Title

      Organic Letters

      Volume: 18 Issue: 17 Pages: 4380-4383

    • DOI

      10.1021/acs.orglett.6b02134

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Presentation] 酸素や水素の脱離を伴う官能基化芳香族化合物の触媒的な迅速合成2019

    • Author(s)
      村井征史
    • Organizer
      第8回化学フロンティア研究会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] gem-二クロムメタン反応剤のアルキンへの付加を伴う1,6-エンインの環化反応2019

    • Author(s)
      村井征史、谷口竜治, 髙井和彦
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Rhenium-Catalyzed Intermolecular anti-Markovnikov Addition Reaction of 1,3-Dicarbonyl Compounds with Terminal Alkynes2018

    • Author(s)
      Masahito Murai, Kazuhiko Takai
    • Organizer
      28th International Conference on Organometallic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Iridium-Catalyzed Sequential Silylation and Borylation of Heteroarenes Based on the Regioselective Two Different C-H Bond Activation2018

    • Author(s)
      Masahito Murai, Naoki, Nishinaka, Kazuhiko Takai
    • Organizer
      4th International Symposium on C-H Activation
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Regioselective Homologation of Arenes through Rhenium-Catalyzed Deoxygenative Aromatization of 7-Oxabicyclo[2.2.1]hepta-2,5-dienes2018

    • Author(s)
      Masahito Murai, Takuya Nakagiri, Takuya Ogita, Kazuhiko Takai
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Selective Transposition of Double Bonds of Alkenes under Palladium Catalysis2018

    • Author(s)
      Kengo Nishimura, Masahito Murai, Kazuhiko Takai
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Rhenium-Catalyzed anti-Markovnikov Addition Reaction of Carbon Nucleophiles to Unactivated Terminal Acetylenes2018

    • Author(s)
      Masahito Murai, Kazuhiko Takai
    • Organizer
      14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] レニウム触媒による7-オキサビシクロ[2.2.1]ヘプタ-2,5-ジエンの脱酸素反応を利用する位置選択的なπ共役系の拡張2018

    • Author(s)
      荻田拓哉、村井征史、髙井和彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Selective Functionalization of Hydrocarbons Based on the Generation of Reactive Organometallic Species2018

    • Author(s)
      村井征史
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] gem-二クロムシリルメタン錯体の構造解析と触媒反応への利用2017

    • Author(s)
      谷口竜治、細川直輝、三町博子、村井征史、押木俊之、髙井和彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京(慶應大学)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 塩化クロム(II)を用いるアルケンの立体選択的ボリルシクロプロパン化反応2017

    • Author(s)
      水田知里、村井征史、髙井和彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京(慶應大学)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] レニウム触媒によるオレフィンの二重結合の選択的な移動反応2017

    • Author(s)
      西村謙吾、村井征史、髙井和彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京(慶應大学)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] レニウム触媒による2-アルケニルフェノールとアルキンの付加反応によるベンゾピラン誘導体の合成2017

    • Author(s)
      山本真輝、村井征史、髙井和彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京(慶應大学)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 位置選択的な炭素-水素結合の活性化によるヘテロ芳香環の連続的なケイ素化-ホウ素化反応2017

    • Author(s)
      西中直樹、村井征史、髙井和彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      東京(慶應大学)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] イリジウム触媒によるヘテロ芳香環のC-H結合の位置選択的ケイ素化-ホウ素化反応2017

    • Author(s)
      西中直樹、村井征史、髙井和彦
    • Organizer
      第111回有機合成シンポジウム2017年 春
    • Related Report
      2017 Research-status Report
  • [Presentation] ジアミン配位子により安定化されたgem-二クロムメタン錯体の反応性と触媒反応への利用2017

    • Author(s)
      Ryuji Taniguchi, Naoki Hosokawa, Masahito Murai, Kazuhiko Takai
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] イリジウム触媒によるシクロプロパン環の位置選択的な開裂を伴うヒドロシリル化反応2017

    • Author(s)
      Masahito Murai, Atsushi Nishiyama, Naoki Nishinaka, Haruka Morita, Kazuhiko Takai
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 金属触媒を用いた炭化水素の効率的な機能化法の開発2017

    • Author(s)
      村井征史
    • Organizer
      第13回触媒相模セミナー
    • Related Report
      2017 Research-status Report
    • Invited
  • [Presentation] Rhenium-Catalyzed anti-Markovnikov Addition Reaction of Carbon Nucleophiles to Unactivated Terminal Acetylenes2017

    • Author(s)
      Masahito Murai
    • Organizer
      International Symposium on Pure & Applied Chemistry
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Regioselective benzoannulation of PAHs via the rhenium-catalyzed deoxygenation of 7-oxabicyclo[2.2.1]hepta-2,5-diene2017

    • Author(s)
      Masahito Murai, Kazuhiko Takai
    • Organizer
      International Symposium on JST ACT-C Project
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Transition Metal-Catalyzed Intermolecular Dehydrogenative Silylation of Aromatic Compounds without Directing Groups Based on the Regio- and Chemoselective C-H Bond Activation2017

    • Author(s)
      Masahito Murai
    • Organizer
      8th Annual Global Congress of Catalysis 2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ロジウム触媒による脱水素を伴う炭素-水素結合のケイ素化反応を経るシラ[n]ヘリセンの合成2016

    • Author(s)
      Masahito Murai, Ryo Okada, Kazuhiko Takai
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      東京(早稲田大学)
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] レニウム触媒による1,3-ケトエステルの末端アルキンへの逆Markovnikov型付加反応2016

    • Author(s)
      植村恵理香、堀駿介、村井征史、髙井和彦
    • Organizer
      第33回有機合成化学セミナー
    • Place of Presentation
      北海道(ヒルトンニセコビレッジ)
    • Year and Date
      2016-09-06
    • Related Report
      2016 Research-status Report
  • [Presentation] Mechanistic insights into the construction of chiral spiro-9-silabifluorenes via the rhodium-catalyzed dehydrogenative silylation2016

    • Author(s)
      Masahito Murai, Yutaro Takeuchi, Kazuhiko Takai
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      京都
    • Year and Date
      2016-07-10
    • Related Report
      2016 Research-status Report
  • [Patent(Industrial Property Rights)] ニトロ基を有する9-シラフルオレン化合物及びその製造方法2018

    • Inventor(s)
      村井征史、髙井和彦
    • Industrial Property Rights Holder
      村井征史、髙井和彦
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2018 Research-status Report

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

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