Photocatalytic Deacylative 1,2-Alkyl(hetero)arylation of Electron-Rich Styrenes

We report a mild photoredox-catalyzed deacylative three-component 1,2-alkyl(hetero)arylation of electron-rich styrenes with unstrained ketone-derived dihydroquinazolinones and electron-rich (hetero)arenes, showcasing high substrate compatibility under oxidative conditions. The radical–polar crossover blueprint uniquely integrates deacylative radical C(sp 3 )–C(sp 3 ) bond formation with polar electrophilic aromatic substitution (S E Ar)-driven C(sp 3 )–C(sp 2 ) bond construction, overcoming competitive N-alkylation and E1-elimination. This method mostly offers a direct route to 1-aryl-1′-heteroarylalkanes and unsymmetrical 1,1-bis(heteroaryl)alkanes.