Takimoto Masanori, Gholap Sandeep Suryabhan, Hou Zhaomin
Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Organometallic Chemistry Laboratory, RIKEN Cluster for Pioneering Research, 2-1 Hirosawa, Wako, Saitama, 351-0198, Japan.
Chemistry. 2019 Jun 21;25(35):8363-8370. doi: 10.1002/chem.201901153. Epub 2019 May 22.
The alkylative carboxylation of ynamides and allenamides with CO and alkylzinc halides catalyzed by a copper catalyst was developed. A variety of alkylzinc halides bearing functional groups were used for this transformation to afford α,β-unsaturated carboxylic acids, which contain the α,β-dehydroamino acid skeleton, introducing the corresponding alkyl group and CO across the carbon-carbon triple or double bond. This alkylative carboxylation formally consists of Cu-catalyzed carbozincation of ynamides or allenamides with alkylzinc halides and the subsequent nucleophilic carboxylation of the resulting alkenylzinc species with CO . This protocol would be a useful method for the synthesis of α,β-dehydroamino acid derivatives possessing a functionalized alkyl group due to the high regio- and stereoselectivity, simple one-pot procedure as well as the use of CO as a starting material.
开发了一种由铜催化剂催化的炔酰胺和烯丙酰胺与一氧化碳和卤化烷基锌的烷基化羧基化反应。各种带有官能团的卤化烷基锌被用于该转化反应，以提供含有α,β-脱氢氨基酸骨架的α,β-不饱和羧酸，通过碳-碳三键或双键引入相应的烷基和一氧化碳。这种烷基化羧基化反应形式上包括铜催化的炔酰胺或烯丙酰胺与卤化烷基锌的碳锌化反应，以及随后生成的烯基锌物种与一氧化碳的亲核羧基化反应。由于具有高区域和立体选择性、简单的一锅法以及使用一氧化碳作为起始原料，该方案将是合成具有官能化烷基的α,β-脱氢氨基酸衍生物的有用方法。
