Ni‐Catalyzed Reductive Acyl Cross‐Coupling: Straightforward Synthesis of α‐Trifluoromethylthiolated Ketones

The trifluoromethylthiol group (‐SCF 3 ) has attracted considerable attention due to its high lipophilicity and strong electron‐withdrawing ability. Over the past decades, numerous methodologies have been developed for the construction of C(sp 2 )–SCF 3 bonds through the selective introduction of the SCF 3 group into arenes or vinyl derivatives. In contrast, the synthesis of tertiary C(sp 3 )‐SCF 3 compounds remains more restricted. Herein, we present a Ni‐catalyzed reductive acyl cross‐coupling that enables the direct construction of α‐trifluoromethylthiolated ketones in a single step utilizing a recently developed SCF 3 ‐containing electrophiles. Moreover, mechanistic investigations have demonstrated the presence of an unusual pathway for reductive coupling and the essential role of zinc.