Preparation of Vicinal Azidohydrins by Reaction of Oxiranes with Triethylaluminium/Hydrogen Azide

A novel, mild, and highly stereoselective transformation of epoxides to azidohydrins by treatment with Et₃Al/HN₃ in toluene is described. As an example for the versatility of the reaction, a polyfunctional compound, 14,15-epoxy-14,15-dihydromilbemycin D ( 1 ), was transformed to 14-azido-14,15-dihydro-15-hydroxymilbemycin D ( 2 ) in 61% yield.