Visible-Light-Driven Radical Cascade Cyclization of 4-(N-Alkyl-N-acrylamido)coumarins: Access to Difluoroalkylated 4,5-Fused Coumarins and Coumarin[4,3-b]pyridinones
Jin-Wei Yuan,*
a Shi-Long Zhang,
a Xin-Ya Wang,
a Meng Yan,
a Xiao-Mei Xiao,
a Dong-Hui Wei *
b and Ling-Bo Qu *
c,d
The article was first published on 27 Mar 2026
Org. Chem. Front., 2026, Accepted Manuscript
https://doi.org/10.1039/D6QO00192K

An efficient and practical visible-light-driven cascade difluoroalkylation/cyclization of 4-(
N-alkyl-
N-acrylamido)coumarins has been developed using readily accessible bromodifluoromethylphosphonium bromide ([Ph
3PCF
2H]
+Br
-) as a difluoromethyl radical precursor. This protocol enables the rapid construction of a wide range of difluoroalkylated 4,5-fused polycyclic coumarin derivatives under mild, additive- and base-free conditions. Moreover, an alternative photoredox-catalyzed intramolecular radical cyclization of 4-(
N-alkyl-
N-acrylamido)coumarins has been established, providing efficient access to structurally diverse coumarin[4,3-
b]pyridinone derivatives. Both transformations proceed smoothly at room temperature, exhibiting broad substrate scope, excellent regioselectivity, and good functional group tolerance. Preliminary mechanistic investigations indicate that the two pathways operate through distinct radical processes involving single electron transfer (SET) and energy transfer (EnT), respectively.