'Salen' along: The iridium(III)–salen complex 1 efficiently catalyzes the title reaction of 2‐ethylbenzenesulfonyl azides to give five‐membered sultams with high enantioselectivity. Other 2‐alkyl‐substitued substrates lead to five‐ and six‐membered sultams with high enantioselectivity; the regioselectivity depends upon the substrate and the catalyst used. EDG=electron‐donating group.