Various chromium(VI)-catalyzed conditions have been tested to improve the oxidation of Delta(5)-steroids with t-BuOOH to their corresponding 5-en-7-ones. The use of PDC or the association of CrO3 with an amine as the catalyst and CH2Cl2 or PhCF3 as the solvent led usually to the best yields. A minor reaction pathway was the epoxidation of the double bond. (c) 2006 Elsevier B.V. All rights reserved.