Zou Long, Zheng Xinyue, Yi XueZheng, Lu Qingquan
The Institute for Advanced Studies, Wuhan University, Wuhan, Hubei, 430072, P. R. China.
Wuhan University Shenzhen Research Institute, Shenzhen, 518000, P. R. China.
Nat Commun. 2024 Sep 7;15(1):7826. doi: 10.1038/s41467-024-52248-y.
Enantioselective transformations of hydrocarbons to three-dimensional chiral molecules remain a significant challenge in synthetic chemistry. This study uses asymmetric paired oxidative and reductive catalysis to promote the enantioselective alkylarylation of olefins through the functionalization of C(sp)-H bonds in alkanes. This asymmetric photoelectrocatalytic approach enables the facile construction of a wide range of enantioenriched α-aryl carbonyls with excellent enantioselectivity (up to 96% ee) from readily accessible starting materials. Notably, aryl bromides, aryl iodides, and even aryl chlorides were compatible with the developed catalytic system. Mechanistic studies reveal that alkanes and electrophiles are simultaneously activated on the electrodes.
在合成化学中，将碳氢化合物对映选择性转化为三维手性分子仍然是一项重大挑战。本研究采用不对称配对氧化和还原催化，通过烷烃中C(sp)-H键的官能团化来促进烯烃的对映选择性烷基芳基化反应。这种不对称光电催化方法能够从容易获得的起始原料出发，轻松构建各种对映体富集的α-芳基羰基化合物，且对映选择性优异（高达96% ee）。值得注意的是，芳基溴化物、芳基碘化物甚至芳基氯化物都与所开发的催化体系兼容。机理研究表明，烷烃和亲电试剂在电极上同时被激活。
