Electrochemical Formation of N-Acyloxy Amidyl Radicals and Their Application: Regioselective Intramolecular Amination of sp2 and sp3 C–H Bonds

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(sp2/sp3)–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.