Zhan Yi-Zhou, Meng Huan, Shu Wei
Shenzhen Grubbs Institute, Department of Chemistry, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology Shenzhen 518055 Guangdong P. R. China
Chem Sci. 2022 Mar 30;13(17):4930-4935. doi: 10.1039/d2sc00487a. eCollection 2022 May 4.
Among the carbo-difunctionalization of alkynes, the stereoselective dialkylation of alkynes is the most challenging transformation due to associated competitive side reactions and thus remains underdeveloped. Herein, we report the first Ni-catalyzed regio- and -selective cross-dialkylation of alkynes with two distinct alkyl bromides to afford olefins with two aliphatic substituents. The reductive conditions circumvent the use of organometallic reagents, enabling the cross-dialkylation process to occur at room temperature from two different alkyl bromides. This operationally simple protocol provides a straightforward and practical access to a wide range of stereodefined dialkylated olefins with broad functional group tolerance from easily available starting materials.
在炔烃的碳双官能化反应中，由于存在竞争性副反应，炔烃的立体选择性二烷基化是最具挑战性的转化反应，因此仍未得到充分发展。在此，我们报道了首例镍催化的炔烃与两种不同烷基溴的区域和立体选择性交叉二烷基化反应，以生成带有两个脂肪族取代基的烯烃。还原条件避免了有机金属试剂的使用，使得交叉二烷基化过程能够在室温下由两种不同的烷基溴发生。这种操作简单的方法提供了一种直接且实用的途径，能够从容易获得的起始原料出发，制备出具有广泛官能团耐受性的多种立体构型明确的二烷基化烯烃。
