Regioselective umpolung addition of dicyanobenzene to α,β-unsaturated alkenes enabled by electrochemical reduction

An umpolung addition of dicyanobenzene to alpha,beta-unsaturated alkenes has been developed using an electroreductive strategy. This electrochemical protocol is well compatible with a broad range of conventionally challenging substrates, including alpha,beta-unsaturated esters, nitriles and trisubstituted enones. Moreover, good to excellent regioselectivities are observed in the reaction of cinnamates with dicyanobenzene. Synthetic utility of this electrochemical approach is further demonstrated by direct late-stage functionalization of (S)-verbenone and 16-dehydropregnenolone acetate.

Automated summary

An umpolung addition of dicyanobenzene to alpha,beta-unsaturated alkenes has been developed using an electroreductive strategy. The electrochemical protocol is compatible with challenging substrates, and good regioselectivities are observed in the reaction. The synthetic utility of this electrochemical approach is demonstrated by direct functionalization of two compounds.