Efficient Functionalisation of Cubic Monovinylsilsesquioxanes <i>via</i> Cross‐Metathesis and Silylative Coupling with Olefins in the Presence of Ruthenium Complexes

Abstract

Abstract Monovinylheptaisobutylsilsesquioxane undergoes efficient cross‐metathesis and silylative coupling with styrenes. Allyl derivatives were successfully tested in cross‐metathesis in the presence of first generation Grubbs’ catalyst, while heteroatom‐substituted vinyl derivatives (vinyl ethers, 9‐vinylcarbazole) efficiently undergo silylative coupling catalysed by ruthenium hydride complexes. Both reactions proceed highly stereoselectively and lead to nearly quantitative formation of E isomers. Only when vinyl ethers are used does the reaction lead to a mixture of stereoisomers. Atmospheric pressure photoionisation has been successfully used for recording mass spectra of the functionalised silsesquioxanes.