Stereodivergent Synthesis of Complex <i>N</i>-Sulfonimidoyl Lactams via the Castagnoli–Cushman Reaction

The reactivity between sulfonimidamide-derived imines and cyclic anhydrides has been investigated. Sulfonimidamide imines readily react with homophthalic anhydride under mild conditions in the presence of non-nucleophilic bases to yield complex lactam products with high diastereoselectivity. Furthermore, it was discovered that sulfonimidamide imines react with homophthalic anhydride in the absence of a base to yield distinct diastereomer products with high diastereoselectivity. Density functional theory calculations suggest the existence of an open transition state pathway in the presence of base and a novel cyclic eight-membered transition state in the absence of base.