21352-91-0Relevant academic research and scientific papers
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.
, p. 6491 - 6500 (2015)
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.
Catalytic Ketone Hydrodeoxygenation Mediated by Highly Electrophilic Phosphonium Cations
Mehta, Meera,Holthausen, Michael H.,Mallov, Ian,Pérez, Manuel,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
, p. 8250 - 8254 (2015/07/07)
Ketones are efficiently deoxygenated in the presence of silane using highly electrophilic phosphonium cation (EPC) salts as catalysts, thus affording the corresponding alkane and siloxane. The influence of distinct substitution patterns on the catalytic effectiveness of several EPCs was evaluated. The deoxygenation mechanism was probed by DFT methods.
