4547-10-8Relevant articles and documents
Hydrosilylation of ketones, imines and nitriles catalysed by electrophilic phosphonium cations: Functional group selectivity and mechanistic considerations
Pérez, Manuel,Qu, Zheng-Wang,Caputo, Christopher B.,Podgorny, Vitali,Hounjet, Lindsay J.,Hansen, Andreas,Dobrovetsky, Roman,Grimme, Stefan,Stephan, Douglas W.
supporting information, p. 6491 - 6500 (2015/04/22)
The electrophilic phosphonium salt, [(C6F5)3PF][B(C6F5)4], catalyses the efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine. [(C6F5)3PCl][B(C6F5)4] and [(C6F5)3PBr][B(C6F5)4] are also synthesised and tested as catalysts. Competition experiments demonstrate that the reaction exhibits selectivity for the following functional groups in order of preference: ketone>nitrile>imine>olefin. Computational studies reveal the reaction mechanism to involve initial activation of the Si-H bond by its interaction with the phosphonium centre. The activated complex then acts cooperatively on the unsaturated substrate. Proceed with cation: The electrophilic phosphonium salt, [(C6F5)3PF][B(C6F5)4], catalyses the efficient hydrosilylation of ketones, imines and nitriles at room temperature. In the presence of this catalyst, adding one equivalent of hydrosilane to a nitrile yields a silylimine product, whereas adding a second equivalent produces the corresponding disilylamine.
Transition metal-catalyzed dehydrogenative silylation of ketones with amine and halide as cocatalysts
Igarashi, Mamoru,Sugihara, Yuichi,Fuchikami, Takamasa
, p. 711 - 714 (2007/10/03)
It was found that dehydrogenative silylation of ketones with hydrosilanes proceeds in the presence of a transition metal catalyst such as palladium on carbon or iridium carbonyl, with amine and halide as cocatalysts, to give the corresponding silyl enol e
