Cp*Rh(iii)-catalyzed electrophilic amination of arylboronic acids with azo compounds for synthesis of arylhydrazides

Abstract

A [Cp*Rh(III)]-catalyzed electrophilic amination of arylboronic acids with diethyl azodicarboxylate (DEAD) was developed, and arylhydrazides were produced in excellent yields and selectivity. The analogous amination with the arylazocarboxylates afforded the corresponding N,N-diarylhydrazides. The electrophilic amination of arylboronic acids with azocarboxylates proceeds readily under mild conditions with excellent functional group tolerance. Up to 99% yields were obtained. Preliminary mechanistic studies revealed that prior formation of an arylrhodium(III) intermediate for the azo coupling reaction can be ruled out.