An efficient procedure for the selective preparation of hydroxy-, carbonyl- and acetal-containing 2-pyrrolidinones has been developed through radical cyclization of 1,6-dienes initiated by α-C(sp3)-H functionalization of alcohols. This protocol could be conducted at catalyst-free conditions at relatively low temperature (80℃) by employing commercially available tert-butyl peroxybenzoate (TBPB) as the oxidant.