Further studies on the synthesis of 24(S),25-epoxycholesterol. A new, efficient preparation of desmosterol

Efforts to improve the synthesis of 24(S),25-epoxycholesterol (1) from stig masterol (3) have included identification of 6 alpha-hydroxy-i-steroid 11 a s 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 acetat e 31 to give 73% of 16, in the most efficient conversion yet of a C22 inter mediate to desmosterol (5) or its acetate 6.