Electro-Oxidative C–C Alkenylation by Rhodium(III) Catalysis

Electrochemical C–C activations were accomplished by expedient oxidative rhodium(III) catalysis. Thus, oxidative C–C alkenylations proved viable with the aid of electricity, avoiding the use of toxic and/or expensive transition-metal oxidants. The chelation-assisted C–C functionalizations proceeded with ample scope and excellent levels of chemo- and position selectivities within an organometallic C–C activation manifold. Detailed mechanistic studies provided support for a kinetically relevant C–C scission, and a well-defined organometallic rhodium(III) complex was identified as a catalytically competent intermediate. The electrochemical C–C functionalization was devoid of additional electrolytes, could be conducted on a gram scale, and provided position-selective access to densely 1,2,3-substituted arenes, which are not viable by C–H activation.