Defluorosilylation of Industrially Relevant Fluoroolefins Using Nucleophilic Silicon Reagents

A number of new magnesium and lithium silyl reagents were prepared and shown to be outstanding nucleophiles in reactions with industrially relevant fluoroolefins. These reactions result in a net transformation of either sp² or sp³ C-F bonds into C-Si bonds by two modes of nucleophilic attack (S_N V or S_N 2'). The methods are mild, proceeding with high chemo- and regioselectivity. Mechanistic pathways are described that lead to new substitution patterns from HFO-1234yf, HFO-1234ze, and HFO-1336mzz, previously inaccessible by transition metal catalyzed difluorosilylation routes.