Base‐Promoted Electrochemical CoII‐catalyzed Enantioselective C−H Oxygenation

• Published in: Angewandte Chemie International Edition 2023-05, Vol.62 (21), p.e202302964-n/a
• Main Authors: Zhou, Gang, Chen, Jia‐Hao, Yao, Qi‐Jun, Huang, Fan‐Rui, Wang, Zhen‐Kai, Shi, Bing‐feng
• Format: Article
• Language: English
• Subjects: Cobalt; C−H Activation; Electrochemistry; Enantiomers; Enantioselectivity; Oxidation; Oxygenation
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202302964

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 CoII‐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 CoIII to CoIV was facilitated by a base and the whole process proceeded through a cobalt(III/IV/II) catalytic cycle. The first electrochemical CoII‐catalyzed enantioselective C−H alkoxylation is reported. A broad range of alkoxylated phosphinamides were obtained in good yields with excellent enantioselectivities (up to 98 % yield and >99 % ee). A cobalt(III) alcohol complex was prepared and characterized, and was found to be a key intermediate in this reaction. Mechanistic studies revealed that the oxidation of CoIII to CoIV was facilitated by a base.