Enantioselective Construction of Tertiary Fluoride Stereocenters by Organocatalytic Fluorocyclization

1,1-Disubstituted styrenes with internal oxygen and nitrogen nucleophiles undergo oxidative fluorocyclization reactions with in situ generated chiral iodine­(III)-catalysts. The resulting fluorinated tetrahydrofurans and pyrrolidines contain a tertiary carbon–fluorine stereocenter. Application of a new 1-naphthyllactic acid-based iodine­(III)-catalyst allows the control of tertiary carbon–fluorine stereocenters with up to 96% ee. Density functional theory calculations are performed to investigate the details of the mechanism and the factors governing the stereoselectivity of the reaction.