Stereoselective syntheses of both enantiomers of ketoconazole (1) from commercially available (R)-or (S)-epichlorohydrin has been developed. The key-step of these syntheses involves the selective substitution of the methylene chlorine atom by benzoate on a mixture of (2S, 4R)-14a and (2R, 4R)-15a or of their enantiomers, followed by crystallization of the corresponding cis-benzoates,(2S, 4R)-18 or (2S, 4S)-18, from which (+)-or (−)-1 were ...
