Enantioselective Lewis base catalyzed phosphonyldifluoromethylation of allylic fluorides using a <i>C</i> -silyl latent pronucleophile
You Zi, Markus Lange, Ivan Vilotijević
Abstract
The first enantioselective phosphonyldifluoromethylation is enabled by the use of diethyl (difluoro(trimethylsilyl)-methyl)phosphonate reagent as a latent pronucleophile in the Lewis base catalyzed substitution of allylic fluorides. The reaction proceeds as a kinetic resolution to produce both the difluoromethylphosphonate products and the remaining fluorides in good yields and with high stereoselectivity. The use of cinchona based alkaloid catalysts enables the facile synthesis of both enantiomers of the difluoromethylphosphonate products.
Topics & Concepts
Allylic rearrangementEnantioselective synthesisChemistryKinetic resolutionSilylationPhosphonateCinchonaCatalysisLewis acids and basesReagentEnantiomerStereoselectivityTrimethylsilylOrganic chemistrySubstitution reactionBase (topology)Medicinal chemistryMathematicsMathematical analysisFluorine in Organic ChemistryCarbohydrate Chemistry and SynthesisInorganic Fluorides and Related Compounds