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.