Organocatalytic Three-Component 1,2-Cyanoalkylacylation of Alkenes via Radical Relay.

Here, we report an unprecedented regioselective, intermolecular 1,2-cyanoalkylacylation of feedstock alkenes with readily available oxime esters and aldehydes by -heterocyclic carbene (NHC) organocatalysis. The crux of this success is the exquisite control over the radical relay process by an NHC organocatalyst. This protocol offers a general platform for diversity-oriented synthesis of valuable ketonitriles under mild, transition-metal-free, and redox-neutral conditions and highlights its potential in the late-stage functionalization of pharmaceutical architectures and natural products.