Organofluorine compounds are attractive synthetic targets in medicinal chemistry. Considering the importance of a C(sp 3 )-rich three-dimensional structures for drug candidates, fluorine-containing quaternary stereogenic centers represent an appealing structural motif. In fact, a few drug molecules containing this motif have been developed, including the first organofluorine drug molecule, fludrocortisone. In this context, the replacement of an α-hydrogen atom of a carbonyl group with a fluorine atom is a useful strategy to prevent undesired racemization under physiological conditions. A representative example is fluorinated analogues of thalidomide (Scheme 1A). The potassium channel modulator BMS-204352 and solithromycin also feature a fluorine-containing quaternary stereogenic center next to the carbonyl group. The development of efficient synthetic routes to acyclic carbonyl compounds that feature an adjacent fluorine-containing quaternary stereogenic center expands the chemical space of three-dimensional organofluorine molecules. A variety of highly efficient enantioselective electrophilic fluorination reactions and C-C bondformation reactions for fluoroenolate species have been disclosed for the fabrication of fluorine-containing quaternary stereogenic centers, although the scope of enolates that provide the product in high enantioselectivity is restricted to cyclic or 1,3-dicarbonyl compounds (Scheme 1B). The lack of successful examples for the acyclic version could possibly be explained in terms of the difficulties associated with controlling the geometric isomerism of the enolate species. Therefore, we anticipated that the emergence of a class of acyclic stereo-defined fluoroenolates would lead to the development of a novel approach to obtain fluorine-containing quaternary stereogenic centers. Silyl fluoroenolates are ideal candidates on account of their easy handling and the track record of their non-fluorinated congeners for stereoselective synthesis. Our literature survey, however, found only a handful of examples of acyclic silyl fluoroenolates. Furthermore, the enolate geometries of some of them were not defined or controlled.