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2019 Fiscal Year Annual Research Report

金属間相乗作用を活かした多核金属クラスター反応場の創出

Planned Research

Project AreaPrecise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
Project/Area Number 15H05808
Research InstitutionOsaka University

Principal Investigator

真島 和志  大阪大学, 基礎工学研究科, 教授 (70159143)

Project Period (FY) 2015-06-29 – 2020-03-31
Keywords金属多核錯体 / マンガン / セリウム / アミド結合切断 / 光触媒 / カルボン酸 / 脱炭酸
Outline of Annual Research Achievements

本研究は高難度触媒反応の達成を目指して、特異な反応場における触媒反応の開発を進め、従来の均一系触媒(単核金属錯体触媒)と質的に異なる「多核金属錯体触媒」が有する、複数の同種・異種金属により囲まれた反応場、の利用による触媒反応の実現を目的とする。最終年度は、二核や四核の多核マンガン錯体を触媒として用いた、化学的安定性に優れたアミド結合の炭素―窒素結合の切断反応による、中性条件下での第3級アミド分解反応において、反応を加速するための配位子検討を行い、含窒素系配位子が反応速度に与える影響を明らかにした。さらに、アミド分解反応の条件に対し、カリウム塩を添加することで触媒活性が劇的に向上し、基質適用範囲が広く高活性な触媒として作用するマンガンーカリウム異種多核錯体が反応中で生じていることを見出した。
さらに、カルボキシラート配位子により架橋された多核金属錯体が示す触媒特性に関して検討を進める中で、カルボキシラート配位子、ならびに酸素架橋により形成される6核錯体の中で、セリウムからなる6核錯体が青色LED光の照射により光触媒として作用し、セリウム-カルボキシラート結合の均一開裂によってカルボキシルラジカルを与えること、また、酸素雰囲気下、脂肪族カルボン酸を用いて青色LED光を照射すると、触媒的な脱炭酸-酸素化反応がすみやかに進行することを明らかにした。従来の光触媒は単核の貴金属錯体が中心として用いられてきたが、今回、多核構造を用いることで、卑金属においても有用な光触媒となりうることを実証した。また、オルトトルイル酸などの安息香酸誘導体を用いた場合には、カルボキシルラジカルが生成した後に水素引き抜き反応が進行し、最終生成物としてラクトンを与えるなど、有機合成上、有用な分子変換反応に応用可能であることを明らかにした。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

  • Research Products

    (55 results)

All 2020 2019 Other

All Int'l Joint Research (4 results) Journal Article (11 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 11 results) Presentation (37 results) (of which Int'l Joint Research: 19 results,  Invited: 4 results) Remarks (1 results) Funded Workshop (2 results)

  • [Int'l Joint Research] ETH Zurich(スイス)

    • Country Name
      SWITZERLAND
    • Counterpart Institution
      ETH Zurich
  • [Int'l Joint Research] UC Berkeley/University of Minnesota(米国)

    • Country Name
      U.S.A.
    • Counterpart Institution
      UC Berkeley/University of Minnesota
  • [Int'l Joint Research] RWTH Aachen/University of Tubingen(ドイツ)

    • Country Name
      GERMANY
    • Counterpart Institution
      RWTH Aachen/University of Tubingen
  • [Int'l Joint Research] Stockholm University(スウェーデン)

    • Country Name
      SWEDEN
    • Counterpart Institution
      Stockholm University
  • [Journal Article] Cobalt‐Catalyzed E‐Selective Cross‐Dimerization of Terminal Alkynes: A Mechanism Involving Cobalt(0/II) Redox Cycles2020

    • Author(s)
      Ueda Yohei、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 59 Pages: 1552~1556

    • DOI

      10.1002/anie.201913835

    • Peer Reviewed
  • [Journal Article] Synthesis, Structure, and Reactivity of Dicationic Bimetallic Tetrabenzyldihafnium Complexes Bearing a Chelating (2-Hydroxyethyl)amido Ligand2020

    • Author(s)
      Inoue Mariko、Lopez Michael J.、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Organometallics

      Volume: 39 Pages: 614~622

    • DOI

      10.1021/acs.organomet.9b00863

    • Peer Reviewed
  • [Journal Article] Cerium(IV) Carboxylate Photocatalyst for Catalytic Radical Formation from Carboxylic Acids: Decarboxylative Oxygenation of Aliphatic Carboxylic Acids and Lactonization of Aromatic Carboxylic Acids2020

    • Author(s)
      Shirase Satoru、Tamaki Sota、Shinohara Koichi、Hirosawa Keishi、Tsurugi Hayato、Satoh Tetsuya、Mashima Kazushi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Pages: 5668~5675

    • DOI

      10.1021/jacs.9b12918

    • Peer Reviewed
  • [Journal Article] Chromium-catalyzed cyclopropanation of alkenes with bromoform in the presence of 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine2020

    • Author(s)
      Ikeda Hideaki、Nishi Kohei、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Chemical Science

      Volume: 11 Pages: 3604~3609

    • DOI

      10.1039/D0SC00964D

    • Peer Reviewed
  • [Journal Article] Dinuclear manganese alkoxide complexes as catalysts for C?N bond cleavage of simple tertiary N,N-dialkylamides to give esters2019

    • Author(s)
      Nagae Haruki、Hirai Takahiro、Kato Daiki、Soma Shusei、Akebi Shin-ya、Mashima Kazushi
    • Journal Title

      Chemical Science

      Volume: 10 Pages: 2860~2868

    • DOI

      10.1039/C8SC05819A

    • Peer Reviewed
  • [Journal Article] Hydrodehalogenation of alkyl halides catalyzed by a trichloroniobium complex with a redox active α-diimine ligand2019

    • Author(s)
      Nishiyama Haruka、Hosoya Hiromu、Parker Bernard F.、Arnold John、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Chemical Communications

      Volume: 55 Pages: 7247~7250

    • DOI

      10.1039/C9CC03268A

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Asymmetric Hydrogenation of Aryl Perfluoroalkyl Ketones Catalyzed by Rhodium(III) Monohydride Complexes Bearing Josiphos Ligands2019

    • Author(s)
      Bruning Fabian、Nagae Haruki、Kach Daniel、Mashima Kazushi、Togni Antonio
    • Journal Title

      Chemistry ? A European Journal

      Volume: 25 Pages: 10818~10822

    • DOI

      10.1002/chem.201902585

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] α-Diimine-Niobium Complex-Catalyzed Deoxychlorination of Benzyl Ethers with Silicon Tetrachloride2019

    • Author(s)
      Parker Bernard F.、Hosoya Hiromu、Arnold John、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Inorganic Chemistry

      Volume: 58 Pages: 12825~12831

    • DOI

      10.1021/acs.inorgchem.9b01784

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis and Characterization of Alkoxide-Bridged Heterometallic Clusters of Cerium and Copper2019

    • Author(s)
      Tsurugi Hayato、Ikeda Yuri、Shinohara Koichi、Shirase Satoru、Toya Nozomi、Tanaka Shinji、Mashima Kazushi
    • Journal Title

      Inorganic Chemistry

      Volume: 58 Pages: 12565~12572

    • DOI

      10.1021/acs.inorgchem.9b01213

    • Peer Reviewed
  • [Journal Article] Synthesis of Pyridylimido Complexes of Tantalum and Niobium by Reductive Cleavage of the N?N Bond of 2,2′-Azopyridine: Precursors for Early?Late Heterobimetallic Complexes2019

    • Author(s)
      Kawakita Kento、Kakiuchi Yuya、Beaumier Evan P.、Tonks Ian A.、Tsurugi Hayato、Mashima Kazushi
    • Journal Title

      Inorganic Chemistry

      Volume: 58 Pages: 15155~15165

    • DOI

      10.1021/acs.inorgchem.9b02043

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] 4,4′-Bipyridyl-Catalyzed Reduction of Nitroarenes by Bis(neopentylglycolato)diboron2019

    • Author(s)
      Hosoya Hiromu、Misal Castro Luis C.、Sultan Ibrahim、Nakajima Yumiko、Ohmura Toshimichi、Sato Kazuhiko、Tsurugi Hayato、Suginome Michinori、Mashima Kazushi
    • Journal Title

      Organic Letters

      Volume: 21 Pages: 9812~9817

    • DOI

      10.1021/acs.orglett.9b03419

    • Peer Reviewed
  • [Presentation] Salt-free reduction of metal compounds for catalytically active species2019

    • Author(s)
      Kazushi Mashima
    • Organizer
      Karl-Ziegler Symposium at GDCh-Wissenschaftsforum Chemie 2019
    • Int'l Joint Research / Invited
  • [Presentation] Approach to generate new catalytically active species based on the reaction mechanism2019

    • Author(s)
      Kazushi Mashima
    • Organizer
      Wenner-Gren Foundations International Symposium “Mechanistic Homogeneous Catalysis-A Meeting between Theory and Experiment”
    • Int'l Joint Research / Invited
  • [Presentation] Stoichiometric and catalytic metathesis cleavage of N=N bond2019

    • Author(s)
      Kazushi Mashima
    • Organizer
      International Symposium on Olefin Metathesis and Related Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Salt-free reduction of transition metal complexes for generating catalytically active species2019

    • Author(s)
      Kazushi Mashima
    • Organizer
      The 2nd Japan Germany Singapore Trilateral Symposium on Precision Synthesis and Catalysis
    • Int'l Joint Research / Invited
  • [Presentation] Esterification of N,N-dialkyl amides by alkoxy-bridged tetranuclear manganese cluster with N,N-bidentate ligand2019

    • Author(s)
      Haruki Nagae, Takahiro Hirai, Daiki Kato, Shusei Soma, Shin-ya Akebi and Kazushi Mashima
    • Organizer
      ACS Fall 2019 National Meeting & Exposition
    • Int'l Joint Research
  • [Presentation] Protic compounds mediated telomerization of alternating copolymerization of CO2 and epoxides by macrocyclic CeZn3 catalysts2019

    • Author(s)
      Haruki Nagae, Shin-nosuke Akutagawa, Jun Okuda and Kazushi Mashima
    • Organizer
      4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Int'l Joint Research
  • [Presentation] Asymmetric hydrogenation of olefinic substrates catalyzed by monohydride-dichloro rhodium(III) complexes2019

    • Author(s)
      Nagataka Tsujimoto, Kosuke Higashida, Fabian Bruning, Kenya Higashihara, Haruki Nagae, Antonio Togni and Kazushi Mashima
    • Organizer
      4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Int'l Joint Research
  • [Presentation] Chromium-catalyzed cyclopropanation of alkenes with bromoform using 2,3,5,6-tetramethyl-1,4-bis(trimethylsilyl)-1,4-dihydropyrazine2019

    • Author(s)
      Kohei Nishi, Hideaki Ikeda, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      4th International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Int'l Joint Research
  • [Presentation] N,N’-Bis(trimethylsilyl)dihydropyrazine as a salt-free reductant for Ni-catalyzed reductive C-C bond formation of aryl halides2019

    • Author(s)
      Yohei Ueda, Nagataka Tsujimoto, Taiga Yurino, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Int'l Joint Research
  • [Presentation] [2+2+1] Pyrrole synthesis from alkynes and azobenzene via N=N bond cleavage catalyzed by vanadium complexes2019

    • Author(s)
      Yuya Kakiuchi, Kento Kawakita, Evan P. Beaumier, Ian A. Tonks, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Int'l Joint Research
  • [Presentation] Synthesis of ortho-aminoalkylated pyridine derivatives via direct C-H bond aminoalkylation catalyzed by group 3 metal complexes2019

    • Author(s)
      Mariko Inoue, Abhinanda Kundu, Haruki Nagae, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Int'l Joint Research
  • [Presentation] Reduction of nitroarenes for generating arylnitrenes by 1,1'-bis(trimethylsilyl)-1H,1'H-4,4'-bipyridinylidene2019

    • Author(s)
      Hiromu Hosoya, Argha Bhattacharjee, Hideaki Ikeda, Kohei Nishi, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Int'l Joint Research
  • [Presentation] Metathesis cleavage of N=N bond in benzo[c]cinnolines and azobenzenes by ditungsten complexes bearing a metal-metal triple bond2019

    • Author(s)
      Hideaki Ikeda, Kohei Nishi, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Int'l Joint Research
  • [Presentation] Chromium-catalyzed cyclopropanation of alkenes with an organosilicon reductant2019

    • Author(s)
      Hideaki Ikeda, Kohei Nishi, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Reductive transformation of nitroarenes by 1,1'-bis(trimethylsilyl)-1H,1'H-4,4'-bipyridinylidene2019

    • Author(s)
      Hiromu Hosoya, Argha Bhattacharjee, Hideaki Ikeda, Kohei Nishi, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Aerobic catalytic oxidation of alcohols to aldehydes by Schiff-base ligated oxo-bridged dicerium complexes2019

    • Author(s)
      Satoru Shirase, Koichi Shinohara, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Hydrosilylation of benzophenone derivatives catalyzed by a cerium complex with a tridentate nitrogen ligand2019

    • Author(s)
      Koichi Shinohara, Hayato Tsurugi and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Transesterification catalyzed by tetranuclear manganese complexes2019

    • Author(s)
      Daiki Kato, Shin-ya Akebi, Takahiro Hirai, Haruki Nagae and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Alkoxide-bridged manganese multinuclear complexes catalyzed esterification of stable N,N-dialkylamides via C-N bond cleavage2019

    • Author(s)
      Takahiro Hirai, Daiki Kato, Shusei Soma, Shin-ya Akebi, Haruki Nagae and Kazushi Mashima
    • Organizer
      The 20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis
    • Int'l Joint Research
  • [Presentation] Mechanistic Studies for Chromium-catalyzed Cyclopropanation of Alkenes in the Presence of Organosilicon Compounds as a Reductant2019

    • Author(s)
      Hideaki Ikeda; Kohei Nishi; Hayato Tsurugi; Kazushi Mashima
    • Organizer
      錯体化学会第69回討論会
  • [Presentation] 第三級アルコールに優れたマンガン錯体による触媒的エステル交換反応2019

    • Author(s)
      加藤大樹、明比慎也、平井崇裕、長江春樹、真島和志
    • Organizer
      第116回有機合成シンポジウム
  • [Presentation] 第一遷移金属を有するアルコキシ架橋四核錯体を触媒とする第三級アルコールとのエステル交換反応2019

    • Author(s)
      明比慎也、加藤大樹、平井崇裕、長江春樹、真島和志
    • Organizer
      第45回反応と合成の進歩シンポジウム
  • [Presentation] マンガン(II)アルコキシド錯体を触媒とした第三級アミドのエステル化反応2019

    • Author(s)
      平井崇裕、加藤大樹、相馬秀成、明比慎也、長江春樹、真島和志
    • Organizer
      第9回CSJ化学フェスタ
  • [Presentation] α-ジイミン配位子を有するニオブ錯体を触媒としたハロアルカンならびにベンジルエーテルの還元的変換反応2019

    • Author(s)
      細谷 広務・Bernard PARKER・西山 悠・劒 隼人・真島 和志
    • Organizer
      錯体化学会第69回討論会
  • [Presentation] Cerium(III) Complex with a N, N-bis(pentafluorophenyl)diethylenetriamine as a Catalyst for Hydrosilylation of Ketones2019

    • Author(s)
      Koichi SHINOHARA; Hayato TSURUGI; Kazushi MASHIMA
    • Organizer
      錯体化学会第69回討論会
  • [Presentation] Synthesis and Characterization of Dinuclear Benzylhafnium Complexes derived from Benzylation of (2-Hydroxyethyl)imine by Tetrabenzylhafnium2019

    • Author(s)
      Mariko Inoue; Michael J. Lopez; Hayato Tsurugi; Kazushi Mashima
    • Organizer
      錯体化学会第69回討論会
  • [Presentation] セリウムと銅からなる異種多核アルコキシド架橋錯体の合成と電気化学特性2019

    • Author(s)
      池田優里、篠原功一、白瀬賢、劒隼人、真島和志
    • Organizer
      錯体化学会第69回討論会
  • [Presentation] Additives for Telomerization of Alternating Copolymerization of Cyclohexene Oxide with Carbon Dioxide Catalyzed by Macrocycle CeZn3 Clusters2019

    • Author(s)
      Haruki Nagae; Shin-nosuke Akutagawa; Hayato Tsurugi; Jun Okuda; Kazushi Mashima
    • Organizer
      第68回高分子討論会
  • [Presentation] 有機ケイ素化合物を還元剤として用いたクロム触媒によるアルケンとブロモホルムのシクロプロパン化反応2019

    • Author(s)
      池田英晃、西耕平、劒隼人、真島和志
    • Organizer
      第66回有機金属化学討論会
  • [Presentation] セリウムオキソクラスター触媒を用いたカルボン酸の光脱炭酸-酸素化反応2019

    • Author(s)
      白瀬賢、玉木颯太、劒隼人、佐藤哲也、真島和志
    • Organizer
      第66回有機金属化学討論会
  • [Presentation] アゾベンゼンの窒素間二重結合の切断を経るビス(イミド)バナジウム錯体を触媒とするアルキンとアゾベンゼンによる多置換ピロール合成2019

    • Author(s)
      垣内勇哉、 川北健人、 Evan P. Beaumier、 劒隼人、 Ian A. Tonks、真島和志
    • Organizer
      第66回有機金属化学討論会
  • [Presentation] アルコキシ架橋マンガン錯体による触媒的なアミドの炭素-窒素結合切断を経たエステル化反応2019

    • Author(s)
      平井崇裕、加藤大樹、長江春樹、真島和志
    • Organizer
      第8回JACI/GSCシンポジウム
  • [Presentation] セリウム-亜鉛マクロサイクル錯体を触媒とした二酸化炭素とエポキシドの交互共重合における末端制御2019

    • Author(s)
      芥川心之介、長江春樹、Thomas, P. Spaniol、奥田純、真島和志
    • Organizer
      第8回JACI/GSCシンポジウム
  • [Presentation] ビピリジンを触媒とするジボロン誘導体を用いた芳香族ニトロ化合物の還元反応2019

    • Author(s)
      細谷広務、Misal Castro Luis Carlos、劒隼人、真島和志
    • Organizer
      第115回有機合成シンポジウム
  • [Presentation] N,N’-ビス(トリメチルシリル)ジヒドロピラジン誘導体を還元剤とするクロム触媒によるアルケンのシクロプロパン化反応2019

    • Author(s)
      西 耕平、池田 英晃、劒 隼人、真島 和志
    • Organizer
      第115回有機合成シンポジウム
  • [Presentation] ニッケル錯体触媒によるアセトニトリルをシアノ源とする芳香族ハロゲン化物のシアノ化反応2019

    • Author(s)
      辻本長嵩、上田耀平、劒隼人、真島和志
    • Organizer
      第115回有機合成シンポジウム
  • [Presentation] ジエチレントリアミン配位子を有する三価セリウム錯体を用いたカルボニル化合物の触媒的ヒドロシリル化反応2019

    • Author(s)
      篠原功一、劒隼人、真島和志
    • Organizer
      第35回希土類討論会
  • [Remarks] 大阪大学大学院基礎工学研究科真島研究室HP

    • URL

      http://www.chem.es.osaka-u.ac.jp/organomet/

  • [Funded Workshop] 第4回精密制御反応場国際シンポジウム2019

  • [Funded Workshop] 第2回精密合成および触媒に関する日独新加坡3国シンポジウム2019

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Published: 2021-12-27  

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