DBU‐Triggered One‐Pot Domino Transformation of Trifluoromethyl Ketones and Dicyanoalkenes into gem‐Difluoroalkenyl γ‐Lactams

The direct conversion of trifluoromethyl ketones to valuable gem ‐difluoroalkenes remains a synthetically useful but underexplored transformation. Herein, we report a base‐catalyzed, one‐pot domino reaction of trifluoromethyl ketones with dicyanoalkenes, enabling formal dual deoxygenation and defluorination. This protocol affords a diverse range of gem ‐difluoroalkenyl unsaturated γ ‐lactams in yields of 62–95% under mild and operationally simple conditions. A proposed mechanism involves a sequential vinylogous aldol reaction, cyclization, rearrangement, and defluorination.