Xphos ligand and platinum catalysts: A versatile catalyst for the synthesis of functionalized β-(E)-vinylsilanes from terminal alkynes

Hydrosilylation of functionalized terminal arylalkynes with a variety of silanes catalyzed by PtCl2 or PtO2 in the presence of the air-stable and bulky Xphos ligand was investigated. Regardless of the electronic nature (electron withdrawing or donating group) and the position (o, m, p) of the substituents on the aromatic ring, a single β-(E)-styrylsilanes was obtained in good to excellent yields. The regioselectivity of the H-Si bond addition was found to be governed by steric effects induced by the bulky Xphos ligand. A dramatic regioselectivity was also observed when functionalized terminal aliphatic alkynes were employed as a substrate and in these cases regioisomeric β-(E)-vinylsilanes were generated with excellent selectivity.

Graphical abstractTotally regioselective hydrosilylation of functionalized terminal arylalkynes was achieved using PtO2 or PtCl2 associated with the stable and bulky Xphos ligand with various silanes. Regardless of the electronic nature of the substituents on the aromatic ring, a single β-(E)-vinylsilanes was obtained in excellent yields. This chemo- and regioselective procedure is general as it was successfully applied to terminal aliphatic alkynes.Figure optionsDownload full-size imageDownload as PowerPoint slide