Alkylative Carboxylation Catalyzed by Transition Metal Catalysts

2016 Fiscal Year Final Research Report

• Project/Area Number: 26460029
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Chemical pharmacy
• Research Institution: Institute of Physical and Chemical Research
• Principal Investigator: Takimoto Masanori 国立研究開発法人理化学研究所, 侯有機金属化学研究室, 専任研究員 (50312377)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Keywords: 銅触媒 / 二酸化炭素 / 有機亜鉛 / カルボン酸 / デヒドロアミノ酸 / イナミド / アレナミド / カルボメタル化

Outline of Final Research Achievements

The alkylative carboxylation of ynamides and allenamides with dialkylzinc reagents and carbon dioxide using a NHC-copper catalyst has been achieved. A variety of ynamides and allenamides undergo this transformation under mild conditions to afford the corresponding unsaturated carboxylic acids, which contain the dehydroamino acid skeleton. The present alkylative carboxylation formally consists of Cu-catalyzed carbozincation of ynamides with dialkylzinc reagents with the subsequent nucleophilic carboxylation of the resulting alkenylzinc species with carbon dioxide. It was also found that the carbozincation of ynamides or allenamides with alkylzinc halides and the subsequent carboxylation of the resulting alkenyl zinc species proceed smoothly in the presence of copper(I) acetylacetonate as the catalyst. In this stepwise transformation, alkylzinc halides bearing functional groups can be used to introduce a functionalized alkyl group to the carboxylation products.

Free Research Field

有機合成化学