A practical and eco-friendly strategy for the radical-mediated decarboxylative [3 + 2] and [4 + 2] annulation of enynals and γ,σ-unsaturated N-(acyloxy)­phthalimides through the photoactivation of an electron donor–acceptor (EDA) complex has been developed. A wide range of primary, secondary, and tertiary alkyl N-hydroxyphthalimide (NHP) esters can be used as suitable substrates for the synthesis of fused ketones without any transition-metal catalysts or oxidants. This protocol features a broad substrate scope, excellent selectivity, and clean reaction conditions.

A novel photoredox-catalyzed C(sp3)-C(sp3) cross-coupling between N-arylamines and cycloketone oxime esters under mild conditions has been accomplished. The redox-neutral reaction proceeds good functional group tolerance and excellent regioselectivity without any...