A process for preparing 15-oxygenated sterols, such as 3.beta.-hydroxy-5.alpha.-cholest-8(14)-ene-15 one, comprising converting 7-dehydrocholesterol to 3.beta.-benzoyloxycholesta-5,7-diene, converting the 3.beta.-benzoyloxycholesta-5,7-diene to a 3.beta.-benzoyloxy-5-cholesta-7,14-diene, converting the 3.beta.-benzoyloxy-5-cholesta-7,14-diene to a 3.beta.-benzoyloxy-14.alpha., 15.alpha.-epoxy-5-cholest-7-ene and converting the 3.beta.-benzoyloxy-14.alpha., 15.alpha.-epoxy-5-cholest-7-ene to a 15-oxygenated sterol. Preferably, the 3.beta.-benzoyloxy-cholesta-5,7-diene is converted to a 3.beta.-benzoyloxy-5-cholesta-7,14-diene by (i) contacting 3.beta.-benzoyloxy-cholesta-5,7-diene, in a solvent at a temperature of at most about -55.degree. C., with HCl at a concentration of at least about 2.0 M for a time sufficient to convert the 3.beta.-benzoyloxycholesta-5,7-diene to a 3.beta.-benzoyloxy-5-cholesta-7,14-diene; (ii) neutralizing the resultant reaction mixture with a base to prevent formation of a significant amount of 3.beta.-benzoyloxy-5-cholesta-8,14-diene; and (iii) recovering the 3.beta.-benzoyloxy-5-cholesta-7,14-diene.