α‐Substituted N‐acylbornane‐10, 2‐sultams 6, 9, and 10 can be converted into enantiomerically pure ketones 5. 13, and 14, respectively, via a two‐step procedure involving a known mercaptolysis reaction followed by an [Fe(acac)₃]‐mediated coupling of the resulting S‐benzyl thioesters with Grignard reagents. Furthermore, enantiomerically pure aldehydes 23 can be obtained from α‐substituted N‐acylbornane‐10,2‐sultams 6 via a one‐step reduction with (i‐Bu)₂AIH. No epimerization at the α‐chiral center is observed during the cleavage reaction whereby the chiral auxiliary, bornane‐10,2‐sultam 1 or ent‐l, was recovered. By using this methodology, several natural products or precursors thereof can be prepared.