In the presence of cesium fluoride and organosilicon reagent, β,β-disubstituted NH-enesulfinamides undergo stereoselective enesulfinamide-sulfinylimine tautomerization at room temperature, resulting in the formation of α-branched N-sulfinyl ketimines in good yields with high stereoselectivity. A variety of acyclic ketone surrogates α-substituted with two electronically and sterically similar groups (e.g., methyl and ethyl), which are typically challenging to access through conventional protocols involving stereoselective protonation of enolates and their equivalents, have been effectively synthesized.