Myriocin (thermozymocidin, ISP-I), which was known to exhibit several interesting biological properties such as potent immunosuppressive and antifungal activities, and a new analog Z-myriocin were synthesized from 2-deoxy-D-glucose. This synthetic pathway comprises a stereoselective formation of the chiral α, α-disubstituted amino acid structure in myriocin and Z-myriocin from the isopropylidene six-menbered ketone by using a modified Darzen reaction as its key step.