Tomasz J Idzik, Magdalena M Lubowicz, Łukasz Struk, Julia Zach, Burkhard König, Jacek G Sośnicki
An effective method with broad substrate scope has been developed for synthesizing C4-arylated C6-hydroxylated δ-lactams containing a quaternary C5 center. The transformation proceeds under photoredox-catalytic conditions via a visible-light-driven, metal-free cascade that includes arylation of β,γ-unsaturated δ-lactams followed by an aza-semipinacol rearrangement. This study reports the retro-aza-semipinacol rearrangement for the first time.