Catalyst‐Directed Selectivity in Vinylcarbene Reactions: A Comparative Study of Ag, Rh, and Cu Complexes

A comprehensive mechanistic investigation is conducted to uncover the factors governing the selectivity of Ag, Rh, and Cu catalysts in vinylcarbene‐mediated reactions. The study examines the preference for carbenic versus vinylogous C(sp 3 )H bond insertion, highlighting the critical roles of the electronic and steric properties of transition metal catalysts. Contrary to previous assumptions that the enhanced electrophilic character of the vinylogous position in metal vinyl carbenes is the primary determinant, the findings demonstrate that the stereoelectronic effects of the ligand play a more dominant role. These insights inform the design of catalytic systems with tailored selectivity, advancing predictive catalysis and CH bond functionalization.