Corticosteroid 9, 11β-epoxides are key intermediates in the preparation of pharmaceutically important compounds such as betamethasone, mometasone, beclomethasone, and dexamethasone. A new process for the 9, 11β-epoxide was developed using a PCl5- mediated regioselective dehydration of 11α-hydroxysteroid to form the corresponding Δ9, 11 double bond. The olefin is then converted into 9α, 11β-bromoformate by treatment with 1, ...