Diastereoselective α‑Fluorination of <i>N</i>-<i>tert</i>-Butanesulfinyl Imidates

A diastereoselective α-fluorination of <i>N</i>-<i>tert</i>-butanesulfinyl imidates was developed. Deprotonation of <i>N</i>-<i>tert</i>-butanesulfinyl imidates with lithium hexamethyldisilazide generates aza-enolates that can be intercepted, with excellent diastereocontrol, by the inexpensive electrophilic fluorinating agent NFSI. This protocol was applied to the preparation of synthetically useful <i>trans</i>-2-fluoro-cyclohexamine with high enantiomeric purity (99.5% ee).