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The first highly enantioselective nucleophilic addition reaction of phosphites with 2H‐azirines has been developed. The reaction was applied to various 3‐substituted 2H‐azirines using novel chiral bis(imidazoline)/ZnII catalysts to afford products in good yield with high enantioselectivity. The transformation of the obtained optically active aziridines showed that 2H‐azirines act as either α,β‐ or...
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