Umpolung α-Silylation of Cyclopropyl Acetates via Low-Temperature Catalytic C–C Activation

We report a redox-neutral, catalytic C-C activation of cyclopropyl acetates to produce silicon-containing five-membered heterocycles in a highly region-and chemoselective fashion. The umpolung -selective silylation leading to dioxasilolanes is opposed to contemporary -selective C-C functionalization protocols of cyclopropanols. Lewis base activation of dioxasilolanes as -silyl carbinol equivalents undergoes the unconventional [1,2]-Brook rearrangement to form tertiary alcohols. Notably, mechanistic studies indicate that an electrophilic metal- interaction harnessing highly fluorinated catalyst permitted a low-temperature C-C activation.