40168-46-5Relevant academic research and scientific papers
Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes
Coles, Nathan T.,Gasperini, Danila,King, Andrew K.,Mahon, Mary F.,Webster, Ruth L.
, p. 6102 - 6112 (2020/07/21)
A detailed synthetic investigation into the dehydrocoupling of silanes with amines, phosphines, and alcohols using an iron precatalyst (1) is presented. We have furnished over 30 examples of aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N-H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed in depth. Beyond this we have explored the substrate scope of phosphinosilane formation which shows a preferential heterodehydrocoupling to give the phosphinosilane with primary and secondary silanes. Silylethers can also be prepared and alcohols that contain alkene functionality do not show any tendency to reduce the double bond.
Si-N Heterodehydrocoupling with a Lanthanide Compound
Cibuzar, Michael P.,Waterman, Rory
supporting information, p. 4395 - 4401 (2019/01/03)
[La{N(SiMe3)2}3THF2] (1) is an effective precatalyst for the heterodehydrocoupling of silanes and amines. Coupling of primary and secondary amines with aryl silanes was achieved with a loading of 0.8 mol % of [L
Tris(oxazolinyl)boratomagnesium-catalyzed cross-dehydrocoupling of organosilanes with amines, hydrazine, and ammonia
Dunne, James F.,Neal, Steven R.,Engelkemier, Joshua,Ellern, Arkady,Sadow, Aaron D.
supporting information; experimental part, p. 16782 - 16785 (2011/12/04)
We report magnesium-catalyzed cross-dehydrocoupling of Si-H and N-H bonds to give Si-N bonds and H2. A number of silazanes are accessible using this method, as well as silylamines from NH3 and silylhydrazines from N2H4. Kinetic studies of the overall catalytic cycle and a stoichiometric Si-N bond-forming reaction suggest nucleophilic attack by a magnesium amide as the turnover-limiting step.
Dehydrocoupling reactions of amines with silanes catalyzed by [(Et2N)3U][BPh4]
Wang, Jia Xi,Dash, Aswini K.,Berthet, Jean Claude,Ephritikhine, Michel,Eisen, Moris S.
, p. 49 - 57 (2007/10/03)
Dehydrocoupling reactions of primary amines RNH2 with PhSiH3 were catalyzed by [(Et2N)3U][BPh4] to give the corresponding aminosilanes PhSiH3-n(NHR)n (n = 1-3), the relative yields of the products were found to be dependent on the experimental conditions and on the nature of R. For a primary silane (PhSiH3), the reactivity of RNH2 follows the order primary > secondary > tertiary. Similar dehydrocoupling reactions using secondary amines with secondary silanes were found to be less reactive. Homodehydrocoupling of the silane was found not to be a competing reaction at room temperature. The hydride [(RNH)2UH][BPh4], which is plausibly formed in the reaction of [(RNH)3U][BPh4] with PhSiH3 is a likely intermediate in the catalytic cycle.
