A versatile rhodium(III) catalyst for direct acyloxylation of aryl and alkenyl C-H bonds with carboxylic acids

作者：Chen, Changjun; Pan, Yixiao; Zhao, Haoqiang; Xu, Xin; Xu, Jianbin; Zhang, Zongyao; Xi, Siqi; Xu, Lijin^*; Li, Huanrong

来源：Organic Chemistry Frontiers, 2018, 5(3): 415-422.

DOI：10.1039/c7qo00844a

• FORMING REDUCTIVE ELIMINATION
• ORTHO-ACETOXYLATION
• ORTHO-BENZOXYLATION
• PALLADIUM(IV) COMPLEXES
• C(SP(2))-H BONDS
• ROOM-TEMPERATURE
• AROMATIC-ACIDS
• ACTIVATION
• FUNCTIONALIZATION
• ARENES

Rh(III)-Catalyzed highly regioselective direct acyloxylation of sp(2) C-H bonds with carboxylic acids has been developed. The catalytic system consisting of a cationic Rh(III) complex and a silver oxidant allowed a variety of arenes and alkenes bearing different directing groups (not limited to strongly coordinating N-heterocyclic directing groups) to undergo efficient acyloxylation with a broad range of readily available alkyl, alkenyl and aryl carboxylic acids, and a number of valuable functional groups in both coupling partners were well tolerated in the reaction regardless of their electronic properties and positions. This method provides a straightforward and convenient access to various valuable acyloxylated products. Furthermore, the synthetic utility of this protocol was demonstrated by the later-stage functionalization and modification of biologically active compounds. Mechanistic studies reveal the involvement of five-membered rhodacycles as key intermediates.

• 出版日期2018-2-7
• 单位中国人民大学