Functionalization of Vinylspherosilicates by Ruthenium-Catalyzed Silylative Coupling Reactions

Highly effective functionalization of monovinylsiloxy heptaisobutylsilsesquioxane and octavinylspherosilicate of the formula (ViMe2SiO)(iBu)7Si8O12 (1) and (ViMe2SiO)8Si8O12 (2), respectively, with a variety of olefins, by using a Ru(H)(Cl)(CO)(PCy3)2‐catalyzed silylative coupling procedure is reported. The cross‐metathesis reaction catalyzed by a ruthenium–carbene complex does not proceed for this system. Whereas the reaction of 1 and 2 with styrene takes place highly stereo‐ and regioselectively, the respective reaction with 1‐hexene gives a mixture of isomers. However, functionalization of 1 and 2 with vinylic heteroatom‐substituted (N, O, Si) derivatives was found to be highly efficient for the synthesis of spherosilicates with β‐heteroatom vinylic functionalities (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)