Asymmetric Nucleophilic Monofluorobenzylation of Carbonyl Compounds: Synthesis of Enantiopure vic‐Fluorohydrins and α‐Fluorobenzylketones

Asymmetric nucleophilic monofluoroalkylation of a broad range of aldehydes with an α‐fluoro‐γ‐sulfinylbenzyl carbanion takes place with complete control of the facial selectivity at the carbanion and good to high anti‐diastereoselectivity to give easily separable mixtures of two optically pure 1,2‐fluorohydrin derivatives (up to 24:1 anti/syn). Separation and removal of the p‐tolylsulfinyl group with tBuLi provides enantiomerically pure anti‐1,2‐disubstituted‐1,2‐fluorohydrins, whereas α‐fluorobenzylketones can be obtained by desulfinylation of the mixture followed by pyridinium chlorochromate oxidation (one‐pot process).