Divergent Synthesis of Enantioenriched beta-Functional Amines via Desymmetrization of meso-Aziridines with Isocyanides

A highly enantioselective ring-opening desymmetrization of meso-aziridines with isocyanides was achieved in the presence of a chiral N,N'-dioxide/Mg(OTf)(2) complex. The in situ generated chiral 1,4-zwitterionic intermediates were successfully trapped by intramolecular oxygen- and carbon-based nucleophiles or exogenous H2O and TMSN3, enabling a collective synthesis of various chiral vicinal amino-oxazoles, spiroindolines, beta-amino amides, and tetrazole derivative in moderate to high yields with excellent enantioselectivities.