Catalyst‐Controlled Regioselective Synthesis of α‐Amino Oxime Esters from N‐(Acyloxy)amides and 2H‐Azirines

Palladium- and rhodium-catalyzed selective reactions of 2H-azirines and N-(acyloxy)amides leading to alpha-amino oxime esters were described. The regioselectivities of the reactions are catalyst-controlled, and two different alpha-amino oxime esters were selectively obtained in high yields. These reactions involved the construction of new N-O and C-N bonds, which are characterized by 100 % atom economy, good to excellent yields, and mild reaction conditions.