Regio- and Stereoselective Hydrosilylation of Unsymmetrical Alkynes Catalyzed by a Well-Defined, Low-Valent Cobalt Catalyst

Alejandro Rivera-Hernandez (1) , Brendan J. Fallon (1) , Sandrine Ventre (1) , Cedric Simon (1) , Marie-Helene Tremblay (1) , Geoffrey Gontard (1) , Etienne Derat (1) , Muriel Amatore (1) , Corinne Aubert (1) , Marc Petit (1, 2)

1 IPCM - Institut Parisien de Chimie Moléculaire
2 CASCH - CAtalysis and Sustainable CHemistry

Herein, the use of a well-defined low-valent cobalt(I) catalyst [HCo(PMe3)(4)] capable of performing the highly regio- and stereoselective hydrosilylation of internal alkynes is reported. The reaction can be applied to a variety of hydrosilanes, symmetrical and unsymmetrical alkynes, giving in many cases a single hydrosilylation isomer. Experimental and theoretical studies suggest the key step to be a hydrocobaltation and that the reaction proceeds through a classical Chalk-Harrod mechanism.

Domaines: Chimie organique

Alejandro Rivera-Hernandez, Brendan J. Fallon, Sandrine Ventre, Cedric Simon, Marie-Helene Tremblay, et al.. Regio- and Stereoselective Hydrosilylation of Unsymmetrical Alkynes Catalyzed by a Well-Defined, Low-Valent Cobalt Catalyst. Organic Letters, 2016, 18 (17), pp.4242-4245. ⟨10.1021/acs.orglett.6b01987⟩. ⟨hal-01397954⟩