Organocatalytic Enantioselective Synthesis of [5.7]-Fused ε-Sultam <i>N</i>,<i>O</i>-Heterocycles via (3 + 2)-Annulation of Seven-Membered Cyclic <i>N</i>-Sulfonylimines with γ-Hydroxy-α,β-Unsaturated Ketones

A highly stereoselective protocol for the (3 + 2)-annulation of biphenyl-bridged seven-membered cyclic <i>N</i>-sulfonylimines with γ-hydroxy-α,β-unsaturated ketones was developed. The reactions afforded a wide range of chiral [5.7]-fused ε-sultams bearing N-adjacent 1,3-stereocenters in excellent yields (93-98% yields) and high enantio/diastereoselectivities (up to >99% ee, >20:1 d.r.) and two other examples with alkoxyl groups were obtained in 52-61% yields, 95% ee, and >20:1 d.r. by utilizing organocatalysis with quinine-derived squaramides.