Affiliation:
1. Center of Chemistry for Frontier Technologies Department of Chemistry Zhejiang University Hangzhou 310027 China
Abstract
AbstractMetalla‐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.
Funder
National Key Research and Development Program of China
National Natural Science Foundation of China
Fundamental Research Funds for the Central Universities
Natural Science Foundation of Zhejiang Province
Subject
General Chemistry,Catalysis
Cited by
48 articles.
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