α-Aminocarbene-Mediated Si-H Insertion: Deoxygenative Silylation of Aromatic Amides with Silanes.

While metal carbene-mediated Si-H insertion reactions have become a powerful strategy to build new C-Si bonds, the utilization of α-aminocarbene intermediates generated from readily available precursors in the Si-H insertion reaction remains a longstanding challenge. Herein, we develop a practical and general strategy to synthesize α-aminosilanes through a deoxygenative cross-coupling of amides and silanes mediated by Sm/SmI 2 . Given the simplicity and versatility, this methodology represents a fascinating example for the effective utilization of inert amides as α-aminocarbene precursors in organic synthesis.