Development of One Step Synthesis of Vinylsilanes from Olefins Catalyzed by Transition Metal

点击翻译按钮获取中文摘要

Vinylsilanes are one of important monomers for the preparation of functinalized materials such as membranes for oxygen enrichment as well as versatile synthetic intermediates in organic synthesis. Conventional method for the preparation of vinylsilanes has been the reaction of acetylenes with hydrosilanes. However, this is not practical method for the production of industrial chemicals, except for the case of the reaction of unsubstituted acetylene with trichlorosilane.The objective of this research project is to develop and establish the highly efficient synthetic method for vinylsilanes from olefins by using new catalytic reactions developed by our group, that is dehydrogenative silylation of olefins with a hydrosilane.1. It was found that a suitable combination of the structures of the olefin, hydrosilane, and catalyst is essential for dehydrogenative silylation to take place. For example, M_3(CO)_<12>(M = Fe, Ru, Os)showed high catalytic activity for the reaction of styrene with triethylsilane. Among them, Fe_3(CO)_<12> showed 100% selectivity, no alkylsilane being obtained as a byproduct. The similar reaction of 1, 5-dienes with triethylsilane was effectively catalyzed by Rh(PPh_3)_3Cl. -2. Ligand effect was examined for ruthenium-catalyzed reaction of styrene with triethoxysilane. Information about the reaction mechanism was collected.In conclusion, it was found that a suitable combination of olefin-catalyst is essential for dehydrogenative silylation to take place. Some practical methods for the preparation of vinylsilanes are established.