Electrophilic Substitution Reaction of Alkenes Using Lewis Acid and Base with Dissociation Equilibrium Properties

2022 Fiscal Year Final Research Report

• Project/Area Number: 20K05504
• 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: Tohoku University
• Principal Investigator: Tanaka Shinya 東北大学, 環境保全センター, 講師 (80570142)
• Project Period (FY): 2020-04-01 – 2023-03-31
• Keywords: Lewis酸 / 塩基 / アルケン / 求電子置換反応 / 酸塩基解離平衡 / Friedel-Crafts反応

Outline of Final Research Achievements

We investigated electrophilic substitution reactions of alkenes by taking advantage of the feature that a base having appropriate bulkiness and basicity is compatible with a Lewis acid without deactivating each other because they can form a reversible Lewis pair. As a result, we found alkylation, formylation, and phosphination of alkenes. Also, the combined use of AgOTf/pyridine was found to be effective for the formylation and phosphinolation. Moreover, We achieved catalytic acylation of alkenes by using InCl3 and carboxylic anhydrides.

Free Research Field

有機合成化学

Academic Significance and Societal Importance of the Research Achievements

アルケンの求電子置換反応は，プロトン脱離が自発的に起こらないために，一般的には進行しない．これに対し本研究では，適切なLewis酸・塩基の組み合わせを用いることで種々のアルケンの置換反応を達成した．本コンセプトはアルケンの求電子置換反応を一般に行う方法論となるものであり，基礎化学的な意義が大きい．また，高価な遷移金属を用いない反応の開発は，持続可能な開発を目指す社会にとって重要である．