Catalyst-free amination of α-cyanoarylacetates enabled by single-electron transfer

A radical benzylic amination of α-cyanoarylacetates without the assistance of any transition-metal catalysts or external photosensitizers was realized. This protocol is operationally simple, mild and of high efficiency. The products could be easily transformed to useful vicinal diamines and α-amino amides. DFT calculations revealed the origin of benzylic rather than aromatic amination regioselectivity in the present reaction.