Selective hydrosilylation of 1,3-diynes catalyzed by titania-supported platinum

Titania-supported platinum (mainly as Pt(II)) has been found to effectively catalyze the hydrosilylation of 1,3-diynes at 70 °C with low catalyst loading (0.25 mol %) under solvent-free conditions. Monohydrosilylation was achieved for diaryl-substituted diynes, whereas dialkyl-substituted diynes were transformed into the corresponding dihydrosilylated products in good yields. In every case, the process was proven to be highly stereoselective, with syn addition of the silicon–hydrogen bond, and regioselective, with the silicon moiety exclusively bonded to the most internal carbon atom of the 1,3-diyne (β-E product), as confirmed by X-ray crystallography.

This work was generously supported by the Spanish Ministerio de Ciencia e Innovación (MICINN; CTQ2007-65218, CTQ2011-24151, and Consolider Ingenio 2010-CSD2007-00006), the Generalitat Valenciana (GV; PROMETEO/2009/002 and PROMETEO/2009/039), and FEDER. Y.M. thanks the ISO of the Universidad de Alicante for a grant. R.B. acknowledges the Universidad de Alicante, CAM, and Union Fenosa for his grant (UF2007-X9159987F).