We describe a visible-light photoredox-catalyzed alkylation/arylative cyclization of N-acrylamides�from 2-arylindoles, 2-arylbenzimidazoles, or N-substituted anilines�with ketone-derived dihydroquinazolinones, accessing indolo-and benzimidazolo[2,1-a]isoquinolines or 2-oxindoles. The consecutive incorporation of alkyl-and aryl-carbogenic motifs across a C=C bond via formal cleavage of ketone α-C−C and arene C−H bonds leads to the formation of five-and six-membered rings, with an allcarbon quaternary stereocenter. This dicarbofunctionalization elaborates aromatization-driven radical C−C functionalization of unactivated aliphatic ketones to construct diverse cyclic structures with functionality tolerance.

A visible-light-photocatalyzed 1,2-arylalkylation of N-(arylsulfonyl)acrylamides with ketone-based dihydroquinazolinones is described. The formal C–C bond cleavage of aliphatic ketones is unified with tandem radical alkylation/1,4-aryl migration/desulfonylation to forge two different types of vicinal C–C bonds and construct an all-carbon quaternary α-stereocenter, thus enhancing the carbogenic complexity and tolerating diverse functionalities. Additional to telescopic synthesis and product diversification, this method features a radical dicarbofunctionalization of conjugated N-(arylsulfonyl)acrylamides with a nucleophilic alkyl radical precursor (dihydroquinazolinone) utilizing oxygen as a green oxidant at ambient temperature.