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

2020 Fiscal Year Final Research Report

• Project/Area Number: 19K15561
• Research Category: Grant-in-Aid for Early-Career Scientists
• Allocation Type: Multi-year Fund
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Nagoya 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
• Keywords: 金属配位子協働作用 / π-供与性配位子

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.

Free Research Field

有機金属化学

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。