Base‐Promoted Electrochemical Co<sup>II</sup>‐catalyzed Enantioselective C−H Oxygenation
Gang Zhou, Jiahao Chen, Qi‐Jun Yao, Fan‐Rui Huang, Zhen‐Kai Wang, Bing‐Feng Shi
Abstract
Abstract Metalla‐electrocatalyzed C−H oxygenation represents one of the most straightforward and sustainable approaches to access valuable oxygenated molecules. Despite the significant advances, the development of enantioselective electrochemical C−H oxygenation reaction is very challenging and remains elusive. Herein, we described the first electrochemical Co II ‐catalyzed enantioselective C−H alkoxylation. A broad range of enantioenriched alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up to 98 % yield and >99 % ee). An unusual cobalt(III) alcohol complex was prepared and fully characterized, which was proven to be a key intermediate of this C−H alkoxylation reaction. Mechanistic studies revealed that the oxidation of Co III to Co IV was facilitated by a base and the whole process proceeded through a cobalt(III/IV/II) catalytic cycle.