syn-Diamination of alkenes using high-valent metal imido complex as a key intermediate

2022 Fiscal Year Final Research Report

• Project/Area Number: 19K05497
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 34010:Inorganic/coordination chemistry-related
• Research Institution: Osaka University
• Principal Investigator: Sugimoto Hideki 大阪大学, 大学院工学研究科, 准教授 (00315970)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Keywords: ナイトレン / アミノ化 / ラジカル

Outline of Final Research Achievements

Various metal complexes in which nitrenes are bound to metal ions were synthesized and characterized by crystal structure analysis, various spectroscopic techniques, and electrochemical analyses. The synthesized metal complexes were reacted with various alkenes in weakly coordinating organic solvents to give the corresponding amine complexes. In experiments using late-transition metal elements, the metal complexes with redox-active aminophenol skeletons and phenylenediamide skeletons were synthesized, and when these complexes were reacted with organic azides as an oxidizing agent, lamination of C(sp3)-H bonds proceeded. We confirmed amination of the C(sp3)-H bond by Sn(II)complexes with phenylenediamido ligands.

Free Research Field

金属錯体化学

Academic Significance and Societal Importance of the Research Achievements

軽炭化水素はシェールガスや原油などの主成分であり、これらを直接的にアミノ化化する方法を開発できれば、これらを原料として天然物や医薬品、あるいは高付加価値を持つ複雑な化合物を合成することが可能となる。本研究成果は、酸化活性種となる金属ーナイトレノイドにラジカル成分を誘起させ、炭化水素の炭素ー水素結合をラジカル的に開裂させ、アミンを生成するものであり、従来の軽炭化水素の変換方法とは異なるものであり、新しい手法を与える。