Group I Alkoxides and Amylates as Highly Efficient Radical Precatalysts for Silicon–Nitrogen Heterodehydrocoupling

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines. The broadly soluble and commercially available KOtAmyl was utilized as the benchmark precatalyst for this transformation. Challenging substrates such as anilines were found to readily couple primary, secondary, and tertiary silanes in high conversions (> 90%) after only 2 h at 40 °C. Traditionally challenging silanes such as Ph3SiH were also easily coupled to simple primary and secondary amines under mild conditions, with reactivity that rivals many rare earth and transition-metal catalysts for this transformation. Preliminary evidence suggests the formation of hypervalent intermediates, but radicals were detected under catalytic conditions, indicating a mechanism that is rare for Si–N bond formation.