Catalyst design and challenging molecular transformations for advanced utilization of first-row transition metals

2022 Fiscal Year Final Research Report

• Project/Area Number: 17H04877
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: The University of Tokyo (2020-2022); Hokkaido University (2017-2019)
• Principal Investigator: Iwai Tomohiro 東京大学, 大学院総合文化研究科, 講師 (30610729)
• Project Period (FY): 2017-04-01 – 2022-03-31
• Keywords: 第一周期遷移金属 / 不均一系触媒 / 均一系触媒 / ホスフィン / ビピリジン / カップリング

Outline of Final Research Achievements

Aiming at the advanced utilization of first-row transition metals in organic synthesis, we developed highly active catalysts based on designing reaction fields that take advantage of the properties of solids and molecules. With heterogeneous nickel catalysts consisting of polystyrene-cross-linking bisphosphine PS-DPPBz that allowed selective metal monochelation, efficient molecular transformations such as cross-coupling of aryl chlorides with alkyl lithiums and decarboxylation of aryl carbamates for aniline synthesis were developed. Moreover, we designed and synthesized dumbbell-shaped bipyridine ligands that promotes nickel-catalyzed one-electron transfer coupling, and their utilities were demonstrated in cross-electrophilic coupling between aryl bromides and alkyl bromides.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

第一周期遷移金属は地球上に豊富に存在することから、環境調和型有機合成の観点で魅力的であるが、凝集や不均化によって失活しやすく、その利用には制限があった。本研究では、固体や分子の特性を活かした反応場設計に基づく第一周期遷移金属触媒の高活性化を達成し、既存系を凌駕する高効率反応や新規分子変換反応の開発に成功した。本成果は、物質生産技術の基礎となる有機合成化学・触媒化学分野の一層の発展に寄与するものである。