Alkylative Carboxylation of Ynamides and Allenamides with Functionalized Alkylzinc Halides and Carbon Dioxide by a Copper Catalyst
Alkylative Carboxylation of Ynamides and Allenamides with Functionalized Alkylzinc Halides and Carbon Dioxide by a Copper Catalyst
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DOI：
10.1002/chem.201901153
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发表时间：
2019-06-21
影响因子：
4.3
通讯作者：
Hou, Zhaomin
中科院分区：
文献类型：
--
作者：
Takimoto, Masanori;Gholap, Sandeep Suryabhan;Hou, Zhaomin
研究了在铜催化剂催化下，用CO2和烷基卤化锌催化酰胺和烯酰胺的烷基化羧化反应。采用多种含官能团的烷基卤化锌进行转化，得到α， β -不饱和羧酸，该羧酸含有α， β -脱氢氨基酸骨架，在碳-碳三键或双键上引入相应的烷基和CO2。这种烷基化羧化反应由铜催化的酰胺或烯酰胺与烷基卤化锌的羧化反应以及随后的烯基锌与二氧化碳的亲核羧化反应组成。该方法具有较高的区域选择性和立体选择性、简单的一锅法以及以CO2为起始原料，可用于合成具有功能化烷基的α， β -脱氢氨基酸衍生物。
The alkylative carboxylation of ynamides and allenamides with CO2 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 alpha,beta-unsaturated carboxylic acids, which contain the alpha,beta-dehydroamino acid skeleton, introducing the corresponding alkyl group and CO2 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 CO2. This protocol would be a useful method for the synthesis of alpha,beta-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 CO2 as a starting material.