Development of C-O Bond Transformation Catalyzed by Functional Dinuclear Complexes for Effective Utilization of Lignin

2022 Fiscal Year Final Research Report

• Project/Area Number: 20K15268
• 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: Hokkaido University
• Principal Investigator: Higashida Kosuke 北海道大学, 化学反応創成研究拠点, 特任助教 (20845466)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Keywords: 協働触媒 / 異種二核錯体 / 量子化学計算

Outline of Final Research Achievements

Homocoupling of methoxy naphthalene derivatives under mild reaction conditions through cleaving nonactivated C-O bonds was achieved with the cooperative catalytic systems of nickel and magnesium metals. The reaction mechanism of the homocoupling was investigated by DFT calculations, in which synergistic effects of nickel and magnesium contributed to cleaving C-O bonds with low energy barrier. Based on these results, novel ligand systems for constructing acid-base cooperative catalysts were developed by using imidazo[1,5-a]pyridinylidene ligand. Design of gold-zinc heterobimetallic complexes was also investigated to produce the effective catalysts for nucleophilic addition of carboxylic acids toward nonactivated alkynes.

Free Research Field

有機金属化学

Academic Significance and Societal Importance of the Research Achievements

触媒を用いた変換反応は、単純な有機反応では実現できない高難度変換反応を具現化し、それによって従来利用が困難であった資源の利用や化学反応の省エネルギー化に貢献することができる。本研究で得られた成果は、石油代替資源として注目されているリグニンに豊富に含まれる不活性なC-O結合を温和に活性化する手法であり、さらに発展させることで未来のエネルギー問題の解決に貢献できる成果といえる。また、本研究で見出した協働作用触媒の雛形となる配位子系は、上記の様な高難度反応を達成する協働作用触媒への応用が期待できることから、学術的のみならず社会への貢献も期待できる成果である。