Efforts to improve the synthesis of 24(S),25-epoxycholesterol (1) from stigmasterol (3) have included identification of 6 alpha-hydroxy-i-steroid 11 as a byproduct from the ozonolysis of 9 and an attempt to effect conversion of sulfone 14 to diol 18 via Payne rearrangement and nucleophilic trapping of epoxide 25, which led instead to 27 and 28 (97% yield). A more efficient synthesis of 1 was achieved via coupling of cuprate 21 with allylic acetate 31 to give 73% of 16, in the most efficient conversion yet of a C22 intermediate to desmosterol (5) or its acetate 6.