Bismuth redox catalysis has been intensively developed in recent years, enabling diverse
transformations that were previously thought to be achievable only through transition
metal catalysis. In this study, we present the desaturation of amides to generate
enamides, an important structural motif in pharmaceuticals, via bismuth photocatalysis.
The protocol involves a combination of unique mechanistic steps recently uncovered
for bismuth thus allowing for the translation of a canonical transition metal-mediated
transformation into a main-group-based catalytic system.