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Chiral-at-metal complex: dynamic asymmetric induction of oxo-vanadium complexes and its application to catalytic asymmetric reactions

Research Project

Project/Area Number 18K14236
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 34010:Inorganic/coordination chemistry-related
Research InstitutionTohoku University (2020)
The University of Tokyo (2018-2019)

Principal Investigator

Nagata Koichi  東北大学, 理学研究科, 助教 (70813830)

Project Period (FY) 2018-04-01 – 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 2019: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2018: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywords金属中心キラル錯体 / 動的不斉誘導 / キラル補助剤 / オキソバナジウム錯体 / 四面体型金属中心キラル錯体 / 鉄錯体 / 不斉反応 / アキラルな配位子 / 金属中心キラリティー / 錯体
Outline of Final Research Achievements

A dynamic asymmetric induction method for tetrahedral metal-centered chiral complexes has been investigated. A tetrahedral complex consisting of four achiral ligands exhibits chirality only at the metal center. By combining the chirality property of the metal center with the properties and metal-specific properties, it is expected that new properties can be expressed in the complex. In this study, we have synthesized oxo-vanadium complexes. First, mononuclear oxo-vanadium complexes with chirality only in the metal center were synthesized, and then, the dynamic asymmetric induction of the oxo-vanadium complexes by chiral auxiliaries was investigated. The dynamic asymmetric induction in solution resulted in only 30-50% de, but one diastereomer was isolated by optical resolution.

Academic Significance and Societal Importance of the Research Achievements

これまでのキラル錯体はキラル配位子を用いる手法が一般的であった。金属中心にのみキラリティーを有する錯体は、安定性などの問題点から八面体構造の錯体に限られており、使用可能な金属に限りがあった。本研究では四面体型金属中心キラル錯体の動的不斉誘導法の確立を目指して研究を行なった。結果として、光学分割により1種類のジアステレオマー体へ誘導することに成功した。今後はエナンチオマー体への誘導を試みる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Research-status Report
  • 2018 Research-status Report
  • Research Products

    (38 results)

All 2021 2020 2019

All Journal Article (4 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 4 results,  Open Access: 4 results) Presentation (34 results) (of which Int'l Joint Research: 6 results,  Invited: 2 results)

  • [Journal Article] Transition-metal Complexes with Triple Bonds to Si, Ge, Sn, and Pb and Relevant Complexes2021

    • Author(s)
      Hashimoto Hisako、Nagata Koichi
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 4 Pages: 778-787

    • DOI

      10.1246/cl.200872

    • NAID

      130008025754

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Asymmetric construction of tetrahedral chiral zinc with high configurational stability and catalytic activity2020

    • Author(s)
      Endo Kenichi、Liu Yuanfei、Ube Hitoshi、Nagata Koichi、Shionoya Mitsuhiko
    • Journal Title

      Nature Communications

      Volume: 11 Issue: 1 Pages: 6263-6263

    • DOI

      10.1038/s41467-020-20074-7

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Ligand effects on the photophysical properties of N,N'-diisopropylbenzimidazolylidene-protected C-centered hexagold(I) clusters2020

    • Author(s)
      Zhen Lei, Koichi Nagata, Hitoshi Ube, Mitsuhiko Shionoya
    • Journal Title

      Journal of Organometallic Chemistry

      Volume: 917 Pages: 121271-121276

    • DOI

      10.1016/j.jorganchem.2020.121271

    • Related Report
      2020 Annual Research Report 2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Creation of POM complexes with multiple bonds between typical elements and transition metals and control of self-assembly2020

    • Author(s)
      Nagata Koichi
    • Journal Title

      Impact

      Volume: 2020 Issue: 4 Pages: 33-35

    • DOI

      10.21820/23987073.2020.4.33

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Asymmetric oxa-Diels-Alder reaction catalyzed by a tetrahedral chiral-at-zinc complex using only achiral ligands』2020

    • Author(s)
      ◯Liu Yuanfei, Kenichi Endo, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis of chiral tetrahedral metal complexes and control of their metal-centered chirality2020

    • Author(s)
      ◯Ayako Hino, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and asymmetric induction of a tetrahedral iron complex with metal-centered chirality2020

    • Author(s)
      ◯Koichi Nagata, Toru Ebihara, Mitsuhiko Shionoya
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] N-Heterocyclic carbene-dased carbon-centered gold-silver clusters with phosphorescence adjustment function2020

    • Author(s)
      ◯Lei Zhen, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric construction of a tetrahedral chiral-at-zinc complex with high configurational stability2020

    • Author(s)
      ◯Kenichi Endo, Liu Yuanfei, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Asymmetric construction of a tetrahedral chiral-at-zinc complex with high configurational stability2020

    • Author(s)
      ◯Masahiro Matsuoka, Koichi Nagata, , Hisako Hashimoto
    • Organizer
      Pacifichem 2021
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] オリゴシロキサンで連結された金属-ケイ素二重結合をもつ二核錯体:合成および1Dチャネル結晶構造2020

    • Author(s)
      ◯中村亮、長田浩一、河津 貴大、松本 和弘、中島 裕美子、橋本久子
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] モリブデンを中心とするカチオン性メタロゲルミレン錯体の合成および小分子との反応2020

    • Author(s)
      ◯松本力也、長田浩一、橋本久子
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Eind基を有するクロムシリリン錯体と共役ジエンおよびα, β-不飽和ケトンとの反応2020

    • Author(s)
      ◯松岡正紘、長田浩一、大野稜真、松尾司、飛田博実、橋本久子
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis of chiral tetrahedral oxovanadium complexes having an achiral unsymmetrical ligand with a bulky substituent and the control of their metal-centered chirality2020

    • Author(s)
      ◯Ayako Hino, Koichi Nagata, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 典型元素-遷移金属元素間に多重結合を有する複合アニオン型分子錯体の創製と展開2020

    • Author(s)
      ◯長田浩一
    • Organizer
      複合アニオン全体会議シンポジウム
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 中性クロムシリリン単核錯体の合成および性質2020

    • Author(s)
      ◯松岡正紘、長田浩一、大野稜真、松尾司、飛田博実、橋本久子
    • Organizer
      第24回ケイ素シンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] N-Heterocyclic Ligands as Regulator of Phosphorescence in Gold(I) and Gold(I)-Silver(I) Clusters2020

    • Author(s)
      ◯Zhen Lei, Koichi Nagata, Xiao-Li Pei, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      The 70th Japan Society of Coordination Chemistry
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Structure of a Chromium Germylyne Complex and Its Reaction with Unsaturated Organic Small Molecule2020

    • Author(s)
      ◯Hirotaka Omura, Koichi Nagata, Hiromi Tobita, Hisako Hashimoto,
    • Organizer
      The 70th Japan Society of Coordination Chemistry
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Properties of a Metallogermylene and Germylyne Complex having Di-substituted Cyclopentadiene Ligand2020

    • Author(s)
      ◯Rikiya Matsumoto, Takahiro Watanabe, Hiromi Tobita, Koichi Nagata, Hisako Hashimoto
    • Organizer
      The 70th Japan Society of Coordination Chemistry
    • Related Report
      2020 Annual Research Report
  • [Presentation] 典型元素-遷移金属元素間に多重結合を有するPOM錯体の創製法の開拓2020

    • Author(s)
      ◯長田浩一
    • Organizer
      複合アニオン全体会議シンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Dynamic Chiral Induction of Tetrahedral Oxo-Vanadium Complexes with a Chiral Metal Center2020

    • Author(s)
      ◯Ayako Hino, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Enantioselective Construction of a Tetrahedral ZnIIABCD Center with a Stable Chirality Sense and a Catalytically Active Coordination Site2020

    • Author(s)
      ◯Kenichi Endo, Liu Yuanfei, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] アキラル配位子からなる四面体型chiral-at-metal錯体の不斉合成と、不斉触媒反応への応用2020

    • Author(s)
      ◯遠藤健一, Liu Yuanfei, 宇部仁士, 長田浩一, 塩谷光彦
    • Organizer
      錯体化学若手の会夏の学校2019
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Properties of a Tetrahedral Chiral-at-Iron Complex bearing a N-Heterocyclic Carbene Ligand2020

    • Author(s)
      ◯Toru Ebihara, Koichi Nagata, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] クロム-ゲルマニウム三重結合をもつ錯体の合成,構造および反応性2020

    • Author(s)
      ◯大村啓貴、長田浩一、飛田博実、橋本久子
    • Organizer
      理学・生命合同シンポジウム2021
    • Related Report
      2020 Annual Research Report
  • [Presentation] 金属中心にキラリティーを有する四面体型オキソバナジウム錯体の合成と動的不斉誘導2020

    • Author(s)
      ◯日野綾子, 長田浩一, 塩谷光彦
    • Organizer
      The 10th CSJ Chemistry Festa 2020
    • Related Report
      2020 Annual Research Report
  • [Presentation] Photochemical Synthesis of a Chromium Germelene Complex and Its Conversion into a Germylyne Complex2020

    • Author(s)
      ◯Hirotaka Omura, Koichi Nagata, Hiromi Tobita, Hisako Hashimoto,
    • Organizer
      日本化学会東北大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis of a Tetrahedral Chiral-at-Iron Complex bearing an Achiral Unsymmetrical Bidentate Ligand and its Elucidation of Properties2020

    • Author(s)
      ◯Toru Ebihara, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Intense Phophorescence in an N-heterocyclic carbene-protected Au(I)-Ag(I) Heterometallic Cluster2020

    • Author(s)
      ◯Lei Zhen, Pei Xiao-Li, Koichi Nagata, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Asymmetric Oxa-Diels-Alder Reaction Catalyzed by a Tetrahedral Chiral-at-Zinc Complex with a Tridentate Achiral Ligand2020

    • Author(s)
      ◯Liu Yuanfei, Kenichi Endo, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 金属中心にキラリティーを持つオキソバナジウム錯体の合成とその動的不斉誘導2020

    • Author(s)
      ◯日野綾子, 長田浩一, 塩谷光彦
    • Organizer
      第69回錯体化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] A Fusion of PPh3 and BPh4-: Property of the 9-phosphatriptycene-10-borate (PTB) anion2020

    • Author(s)
      ◯Koichi Nagata, Marcus W. Drover, Jonas C. Peters
    • Organizer
      第68回錯体化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Synthesis and Dynamic Chiral Induction of Tetrahedral Oxo-Vanadium Complexes with a Chiral Metal Center2020

    • Author(s)
      Ayako Hino, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Enantioselective Construction of a Tetrahedral ZnIIABCD Center with a Stable Chirality Sense and a Catalytically Active Coordination Site2020

    • Author(s)
      Kenichi Endo, Liu Yuanfei, Hitoshi Ube, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Synthesis of a Tetrahedral Chiral-at-Iron Complex bearing an Achiral Unsymmetrical Bidentate Ligand and its Elucidation of Properties2020

    • Author(s)
      Toru Ebihara, Koichi Nagata, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] ntense Phophorescence in an N-heterocyclic carbene-protected Au(I)-Ag(I) Heterometallic Cluster2020

    • Author(s)
      Lei Zhen, Pei Xiao-Li, Koichi Nagata, Hitoshi Ube, Mitsuhiko Shionoya
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] 研究室に配属されてから10年2020

    • Author(s)
      長田 浩一
    • Organizer
      名古屋大学理学部
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] アキラル配位子からなる四面体型chiral-at-metal錯体の不斉合成と、不斉触媒反応への応用2019

    • Author(s)
      遠藤健一, Liu Yuanfei, 宇部仁士, 長田浩一, 塩谷光彦
    • Organizer
      錯体化学若手の会夏の学校2019
    • Related Report
      2019 Research-status Report

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Published: 2018-04-23   Modified: 2022-01-27  

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