An Aza‐Prilezhaev‐Based Method Inverts Regioselectivity in Stereospecific Alkene 1,2‐Aminohydroxylations

Under acidic conditions (TFA) and in the presence of water, BocNHOTs promotes stereospecific 1,2‐aminohydroxylations of alkenes. The processes involve intermolecular aza‐Prilezhaev aziridination followed by stereospecific SN2 opening by water. This reagent combination provides regiochemical outcomes that are opposite to, or more selective than those observed using epoxidation initiated 1,2‐aminohydroxylation protocols. Replacement of water by other nucleophiles allows 1,2‐amino(thio)etherification, diamination, aminoazidation and aminofluorination reactions. Intramolecular processes are also feasible, including unusual variants that evoke azabicyclobutane‐like reactivity.