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

Autor: Zhou, Gang, Chen, Jia‐Hao, Yao, Qi‐Jun, Huang, Fan‐Rui, Wang, Zhen‐Kai, Shi, Bing‐feng
Předmět:
Zdroj: Angewandte Chemie; 5/15/2023, Vol. 135 Issue 21, p1-6, 6p
Abstrakt: 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. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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