Metallaphotoredox catalysis enables facile (trifluoromethyl)thiolation of alkenyl iodides

Abstract

The trifluoromethylthioether (SCF₃) moiety represents a privileged functionality in pharmaceuticals and agrochemistry, however the synthesis and application of alkenyl-SCF₃ compounds remain comparatively nascent. Herein, we demonstrate a nickel (Ni)-catalyzed, photoredox-based approach for the trifluoromethylthiolation of alkenyl iodides to access diverse and biologically relevant alkenyl-SCF₃ compounds under mild and air-tolerant conditions. The developed methodology tolerates a broad range of substituted (hetero)aromatic and aliphatic alkenyl iodides, exhibiting general Z selectivity arising from an in situ photoisomerization mechanism. This process was readily extended to a generalized thiolation protocol through the utilization of diverse, medicinally relevant thiols to provide unique alkenyl sulfide products. The utility of the products was demonstrated by post-functionalization, providing enhanced degrees of molecular complexity in the products.