An Aza-Prilezhaev-Based Method for Inversion of Regioselectivity in Stereospecific Alkene 1,2-Aminohydroxylations

Abstract

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.