Catalytic Reduction of Imines with Silylformates: Formation of Silyl Carbamates through CO ₂ Insertion

Silylformates are emerging surrogates of hydrosilanes, able to reduce carbonyl groups in transfer hydrosilylation reactions, with the concomitant release of CO 2 . In this work, a new reactivity is revealed for silylformates, in the presence of imines. Using ruthenium catalysts, and lithium iodide as a co‐catalyst, imines are shown to undergo hydrocarboxysilylation by formal insertion of CO 2 to the N−Si bond of silyl amine to yield silyl carbamates in excellent yields.