Development of Efficient Aromatic C-H Amination method Using Highly Reactive Hypervalent Iodine Catalyst

2021 Fiscal Year Final Research Report

• Project/Area Number: 19K05466
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 33020:Synthetic organic chemistry-related
• Research Institution: Ritsumeikan University
• Principal Investigator: Dohi Toshifumi 立命館大学, 薬学部, 教授 (50423116)
• Project Period (FY): 2019-04-01 – 2022-03-31
• Keywords: アミノ化 / 酸化 / カップリング / 芳香族化合物

Outline of Final Research Achievements

Due to its straightforward characteristics, oxidative coupling of aromatic compounds with amines recently attracts attention as a synthetic strategy of aromatic amines that are important as a structure of pharmaceutical products and functional materials. In this research, by suggesting and proving a new guideline for the activity enhancement of the hypervalent iodine catalyst,we have developed excellent oxidation organocatalyst even working at 0.1 mol%. During this research, it was revealed and found that our newly developed catalyst is also compatible with electrochemical activation and can function as an electrocatalyst for dearomative spirolactam-forming reactions.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

研究開始当時、芳香環C-Hアミノ化に用いる遷移金属触媒は最低でも5mol%は必要で、触媒活性の向上は難しい状況であった。超原子価ヨウ素触媒についても、我々がこれまで提案した反応性向上の指針のみでは、数mol%程度への触媒量低減が限界であった。触媒性能向上の新指針に基づき、我々が本研究で開発した触媒は、芳香環C-Hアミノ化において0.1mol%の触媒量でも十分に機能する。ヨウ素中心の反応性が高いため、有機触媒としての構造多様化を行っても十分な活性を保持しつつ、立体および化学選択的な触媒の分子設計や機能化へと発展できる。