Acylsilanes in Transition-Metal-Catalyzed and Photochemical Reactions: Clarifying Product Formation.

Acylsilanes are able to react as nucleophilic carbene precursors, electrophiles, and directing groups in C-H functionalization. To date, some of the products reportedly formed during transition-metal-catalyzed and photochemical reactions involving acylsilanes have been incorrectly assigned. To provide clarity, we herein address these structural misassignments and detail the revised structures. New insights into the reactivity of acylsilanes were also afforded via the discovery that light-induced siloxy carbenes participate in intramolecular 1,2-carbonyl addition to proximal esters.