Development of Enantioselective Hunsdiecker-type Reaction

2017 Fiscal Year Final Research Report

• Project/Area Number: 16K13993
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Toyohashi University of Technology
• Principal Investigator: Shibatomi Kazutaka 豊橋技術科学大学, 工学(系)研究科(研究院), 准教授 (00378259)
• Project Period (FY): 2016-04-01 – 2018-03-31
• Keywords: 脱炭酸反応 / 不斉合成 / 有機分子触媒 / 塩素化反応 / ハロゲン化反応 / SN2反応

Outline of Final Research Achievements

Although decarboxylative halogenation of aliphatic carboxylic acids is known to be a useful synthetic method for the preparation of a variety of organohalides, an enantioselective version of this reaction has not been reported so far. In this research, we succeeded in developing a highly enantioselective decarboxylative chlorination of b-ketocarboxylic acids to yield a-chloroketones. The reaction proceeded with high enantioselectivity (up to 98% ee) in the presence of chiral primary amine catalyst. The resulting a-chloroketones could be converted into a-aminoketones and a-thio-substituted ketones via SN2 reactions. Our results offer the first example of enantioselective decarboxylative halogenation of carboxylic acids.

Free Research Field

有機合成化学、有機金属化学、フッ素化学、化学系薬学