Practical and scalable synthesis of bench-stable organofluorosilicate salts

Abstract

Silanes have enjoyed significant success as synthetic tools in the last few decades. In many of the reactions that use silanes, a pentacoordinate silicate is proposed as the reactive intermediate. Despite this, there is no general method to synthesize pentacoordinate fluorosilicates and use them as reagents instead of organo- or alkoxysilanes. Herein, we report the first practical synthesis of organotetrafluorosilicates. The method is tolerant of a number of different functional groups including electrophiles with preferential attack of the fluoride on the silane rather than the electrophile. This transformaton is generally high yielding, even at the mole scale. Furthermore, we demonstrate that organotetrafluorosilicates are both more reactive than the corresponding trialkoxysilanes and more stable under solvolytic conditions. Organotetrafluorosilicates can be used as substrates for a variety of coupling reactions, oxidations, and radical reactions. Overall, organotetrafluorosilicates represent a new platform on which to develop challenging transformations.