Hydrosilylation of ketones, imines and nitriles catalysed by electrophilic phosphonium cations: functional group selectivity and mechanistic considerations

Chemistry : a European Journal
Manuel PérezDouglas W Stephan

Abstract

The electrophilic phosphonium salt, [(C6 F5 )3 PF][B(C6 F5 )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. [(C6 F5 )3 PCl][B(C6 F5 )4 ] and [(C6 F5 )3 PBr][B(C6 F5 )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.

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Citations

Aug 14, 2015·The Journal of Organic Chemistry·Baosheng WeiZhenfeng Xi
May 31, 2016·Angewandte Chemie·Jiangtao ZhuDouglas W Stephan
Apr 1, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·P T K Lee, L Rosenberg
Mar 8, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Kevin M Szkop, Douglas W Stephan
Dec 17, 2015·Dalton Transactions : an International Journal of Inorganic Chemistry·Julia M BayneDouglas W Stephan
Aug 11, 2015·Chemical Society Reviews·J M Bayne, D W Stephan
Feb 26, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Ian Mallov, Douglas W Stephan
Jun 21, 2017·Chemical Communications : Chem Comm·Ian MallovDouglas W Stephan
Feb 28, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Krzysztof DurkaSergiusz Luliński
May 4, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Shawn PostleDouglas W Stephan
Apr 21, 2016·Chemical Communications : Chem Comm·Juri MöbusDouglas W Stephan
Jun 22, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·Renzo Arias UgarteTodd W Hudnall
Oct 26, 2016·Chemistry : a European Journal·Valerio FasanoMichael J Ingleson
Oct 7, 2016·Chemical Communications : Chem Comm·Alessandra AugurusaDouglas W Stephan
Oct 28, 2016·Dalton Transactions : an International Journal of Inorganic Chemistry·James H W LaFortuneDouglas W Stephan
Nov 16, 2016·Chemical Communications : Chem Comm·Kelly F FirthDouglas W Stephan
Jun 18, 2015·Chemical Communications : Chem Comm·Manuel PérezDouglas W Stephan
Nov 15, 2017·Dalton Transactions : an International Journal of Inorganic Chemistry·Alejandro G BarradoManuel Alcarazo
Sep 20, 2016·Angewandte Chemie·Mark C LipkeT Don Tilley
Jun 3, 2015·Angewandte Chemie·Meera MehtaDouglas W Stephan
Aug 29, 2018·Angewandte Chemie·Mengxi YangFrançois P Gabbaï
Jun 6, 2020·Chemistry : a European Journal·Ramkumar KannanAjay Venugopal
Nov 1, 2015·Chemical Science·Daniel WinkelhausDouglas W Stephan
Oct 28, 2018·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Masumi Itazaki, Hiroshi Nakazawa
Nov 21, 2019·Chemical Communications : Chem Comm·Ramkumar KannanAjay Venugopal
Apr 22, 2019·The Journal of Chemical Physics·Eike CaldeweyherStefan Grimme
Apr 30, 2021·Chemical Communications : Chem Comm·Tomoaki TakayamaTakayuki Komatsu
Jun 2, 2015·Journal of the American Chemical Society·Michael H HolthausenDouglas W Stephan
Jul 15, 2015·The Journal of Organic Chemistry·Narasimhulu GandhamsettySukbok Chang
Sep 16, 2021·Journal of the American Chemical Society·Daniel RothLutz Greb

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