Reaction of (bromodifluoromethyl)phenyldimethylsilane with organometallic reagents

A new fluorine-containing organosilicon compound, (bromodifluoromethyl)-phenyldimethylsilane (II), was synthesized by the N-bromosuccinimide (NBS) bromination of difluoromethyl)phenyldimethylsilane (I), which was prepared from phenyldimethylsilyllithium and chlorodifluoromethane. Compound II reacted with dimethyl sulfoxide to give dimethyl sulfide and phenyldimethylfluorosilane in quantitative yield. The reaction of II with nucleophiles, such as sodium ethoxide, Grignard or lithium reagents, afforded products arising from cleavage of the carbonsilicon bond. In contrast, the reaction of II with Grignard reagents in the presence of appropriate catalysts (Group VIII transition metal salts or complexes) afforded the homo-coupling product of II, 1,2-bis-(phenyldimethylsilyl)-1,1,2,2-tetrafluoroethane (IV), in excellent yield. The silver(I) salt-catalyzed reaction of II with ethylmagnesium bromide gave the cross-coupling product, (1,1-difluoropropyl)phenyldimethylsilane (V) as well as III and IV. When cuprous bromide was employed as catalyst, the reaction of II with ethylmagnesium bromide afforded 1-phenyldimethylsilyl-1-propene (VI) and 3-phenyldimethylsilyl-2-pentene (VII) as main products.