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Alkane transformation via 1,2-addition of C-H bods

Research Project

Project/Area Number 19K15561
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNagoya University

Principal Investigator

Nakano Ryo  名古屋大学, 工学研究科, 助教 (30835731)

Project Period (FY) 2019-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords金属配位子協働作用 / π-供与性配位子 / 金属配位子協働触媒 / π供与性配位子 / アルカン変換 / 1,2-付加
Outline of Research at the Start

持続的な炭素資源の運用法の確立は21世紀の化学者に課せられた最も重要な課題の一つである. 石油や天然ガスに豊富に含まれる低級アルカンは従来燃料として用いられて来たが, 官能基化・高級化によって化学原料へと変換する手法の開発が求められる. 本研究では「アルカンC-Hの金属-ヘテロ原子多重結合への1,2-付加」というこれまで用いられて来なかった素反応に着目し, 安価で豊富に存在する卑金属を触媒としてこれらの反応を行う手法の開発を目指す.

Outline of Final Research Achievements

In this study, we have focused on the elementary reaction of 1,2-addition of alkane C-H to metal-heteroatom multiple bonds, which is known with early metals, and have examined the application of this elementary reaction with middle and late metals. First, we developed bidentate and tridentate ligands bearing guanidine moieties and synthesized metal complexes of Fe, Ru, Co, Rh, and Pd. The Rh complex was investigated in detail, and it was found by deuterium labeling experiments, that the metal ligand cooperative C-H activation is possible by deprotonating the guanidine with a strong base. In addition, the π-electron-donating nature of the guanidine moiety was utilized for the first rhodium-catalyzed synthesis of acrylates from carbon dioxide and ethylene.

Academic Significance and Societal Importance of the Research Achievements

C-H結合の直接的変換反応は、従来多段階で行われていた化学変換を1段階で行う効率的な手法であり、広く研究されている。本研究ではその基礎反応であるC-H切断段階に着目した。前周期遷移金属で知られるアルカンC-Hの金属-ヘテロ原子多重結合を1,2-付加を中後周期遷移金属で実現することで、安価で豊富に存在する卑近金属を用いたC-H結合変換反応に繋がる可能性が期待される。また、本研究で扱った強いπ電子ドナーと後周期遷移金属の組み合わせは比較的未開拓な領域であり、この配位子と金属の電子反発を利用した新たな錯体化学を開拓したことも本研究の学術的意義である。

Report

(3 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • Research Products

    (4 results)

All 2021 2020 2019

All Presentation (4 results)

  • [Presentation] Synthesis and reactivity of rhodium and ruthenium complexes bearing a guanidine-based pincer ligand2021

    • Author(s)
      Shinnosuke Takegasa, Ryo Nakano, Makoto Yamashita
    • Organizer
      日本化学会 第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] Acrylate formation from CO2 and ethylene by using rhodium complexes bearing a guanidine-based pincer ligand2021

    • Author(s)
      Shinnosuke Takegasa, Ryo Nakano, Makoto Yamashita
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Application of Cyclic Guanidine-based NCN Pincer Complex2020

    • Author(s)
      Ming Min Lee, Ryo Nakano, Makoto Yamashita
    • Organizer
      日本化学会 第100春季年会(2020)
    • Related Report
      2020 Annual Research Report
  • [Presentation] Ligation Behavior of a Pyridine-Tethered Cyclic Guanidine to Late Transition Metals2019

    • Author(s)
      Ming Min Lee, Ryo Nakano, Makoto Yamashita
    • Organizer
      7th Asian Conference of Coordination Chemistry (ACCC7)
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2022-01-27  

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