Heterodehydrocoupling of Silanes and Amines Catalyzed by a Simple Lanthanum-Based Complex

Abstract

We report an attractive and efficient synthetic approach to form Si–N bonds via the heterodehydrocoupling of silanes and amines catalyzed by a lanthanum-based N,N-dimethylbenzylamine complex [La(DMBA)3]. A wide variety of primary and secondary amines were well-suited coupling partners with primary, secondary, and tertiary silanes for this catalytic transformation, resulting in the formation of numerous silylamines in high efficiency and moderate-to-excellent yields under mild conditions.

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

“…Notably, initial exploration in the reaction between n OcSiH 3 and PhNH 2 indicates that this catalyst may be general for primary silanes with both alkyl and aryl groups. Moreover, catalysis with KO t Amyl greatly enhances the accessibility for aminosilane with substituted aniline groups, which was previously only accessible through heterodehydrocoupling with Schmidt's La(DMBA) 3 [7b] …”

Sustainable preparation of aminosilane monomers, oligomers, and polymers through Si–N dehydrocoupling catalysis

“…In 2022, the Schmidt group reported a considerable amine-silane dehydrocoupling scope using the lanthanum precatalyst, La(DMBA) 3 , where DMBA = N , N -dimethylbenzylamine. 74 Initial attempts to dehydrocouple PhSiH 3 and PhNH 2 using 2.5 mol% of La(DMBA) 3 found pyridine to be an optimal solvent. They proceeded to explore the scope of this reaction with 2.5 mol% of catalyst in pyridine at 50 °C for 16 h, using an optimized 1 : 3.3 silane:amine ratio to minimize product mixtures.…”

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

“…3, top right). 41 The disproportionate reactivity of PyNH toward all silane substrates tested was motivation for not utilizing it as the model amine substrate in optimization reactions and mechanistic studies. 23,31,40 Catalysis with 1 could also be extended to Et 3 SiH.…”