Electrochemical generation of N-acyloxy amidyl radicals via an inner-sphere electron-transfer process is described for the first time. With NaBr as the catalyst and electrolyte, the in situ generated amidyl radicals undergo intramolecular C(sp/sp)-H aminations to give lactams with unprecedented regio- and chemoselectivities. Moreover, the synthetic utility of current method is demonstrated by the synthesis of PJ34 and Phenaglaydon.

Electrochemical fluoromethylation triggered lactonizations of alkenes were achieved under chemical oxidant-, catalyst- and additional supporting electrolyte-free conditions.