Grignard reagents as simple precatalysts for the dehydrocoupling of amines and silanes.

Methyl magnesium bromide is a precatalyst for the dehydrocoupling of silanes and amines to produce aminosilane products under mild conditions. As a commercially available Grignard reagent, this precatalyst represents a simplification over previous magnesium-containing catalysts for Si-N bond formation while displaying similar activity to other magnesium-based catalysts. This observation is consistent with the hypothesis that competitive Schlenk equilibrium can be addressed by not using an ancillary ligand.

Group I Alkoxides and Amylates as Highly Efficient Silicon-Nitrogen Heterodehydrocoupling Precatalysts for the Synthesis of Aminosilanes.

Group I alkoxides are highly active precatalysts in the heterodehydrocoupling of silanes and amines to afford aminosilane products. The broadly soluble and commercially available KO Amyl 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.

Commercially available organolithium compounds as effective, simple precatalysts for silicon-nitrogen heterodehydrocoupling.

A family of commercially available organolithium compounds were found to effectively catalyze the heterodehydrocoupling of silanes and amines under ambient conditions. Ubiquitous BuLi (1) was utilized as the benchmark catalyst, where an array of primary, secondary, and tertiary arylsilanes were coupled to electron-donating amines, affording aminosilanes in high conversions with short reaction times. Preliminary mechanistic analysis is consistent with a nucleophilic-type system that involves the formation of a hypervalent silicon intermediate.