Cp∗Ir(III)-Catalyzed Mild and Broad C-H Arylation of Arenes and Alkenes with Aryldiazonium Salts Leading to the External Oxidant-Free Approach

Abstract

Reported herein is the development of Cp*Ir(III)- catalyzed direct C−H arylation of arenes and alkenes using aryldiazonium tetrafluoroborates, the use of which as an aryl precursor and also as an oxidant via C−N2 bond cleavage was a key to success in achieving a mild and external oxidant-free procedure. Mechanistic experiments and DFT calculations revealed the turnover-limiting step to be closely related to the formation of an Ir(V)-aryl intermediate rather than the presupposed C−H cleavage. Under the developed mild arylation conditions, a wide range of benzamides were smoothly arylated. In addition, synthetic utility of the current C−H arylation procedure was also demonstrated successfully for the (Z)-selective arylation of enamides and C8-selective reaction of quinoline N-oxides. © 2015 American Chemical Society