Diastereoselective synthesis of cyclopropyl sulfoxides <i>via</i> hydrosulfenation

Cyclopropyl sulfoxides, merging two privileged motifs in medicinal chemistry, remain synthetically challenging despite their pharmaceutical potential. Herein, we report a mild, metal-free hydrosulfenation strategy that enables their direct synthesis, achieving exceptional diastereoselectivity (dr up to > 20 : 1) in systems with up to eight possible diastereomers. Chiral sulfoxides with 4 to 7 stereogenic centers were also synthesized in high dr. The methodology provides direct access to medicinally relevant architectures, including cyclopropyl sulfones, sulfoximines, and drug-conjugated hybrids. Mechanistic studies reveal stereochemical control <i>via</i> collective spatial factors including <i>endo</i>/<i>exo</i>, facial and side selectivities during the cycloaddition step.