Reaction of sulfinamides with in situ generated N‐trifluoromethanesulfonyl ketimines occurs rapidly at room temperature in the presence of KOt‐Bu. The precursor N‐H imines are accessible by organolithium addition to nitriles or condensation of HMDS with ketones. This protocol avoids work‐up and reactor cleaning challenges encountered in the traditional Ti(OEt)4 mediated condensation approach. The reaction works well for extremely hindered substrates, some of which were inaccessible with the Ti(OEt)4 procedure.