Abstract The reaction of 1-hydrohexafluoroisobutenyloxytrimethylsilane (2a) with cesium fluoride in diglyme leads to elimination of trimethylfluorosilane to form the 1- hydrohexafluoroisobutenolate anion (3), which is silylated with trialkylchlorosilanes at the oxygen atom. In the presence of bis (trifluoromethyl) ketene N, N, O-trimethylaminoacetal or N-(α, α-difluoroalkyl)-dialkylamines, silane 2a is transformed into 2, 2, 2', 2'-tetrakis ( ...