Synthesis of the Trans and Cis Higher Sugar Allylic Alcohols—Direct Precursors of Dodecoses

Abstract

Reaction of 6,7-dideoxy-l,2:3,4-di-O-isopropylidene-α-D-galacto-hept-6-ynopyranose (3) with 3-O-benzyl-l,2-O-sopropylidene-α-D-xylo-pentodiulose (4) afforded two diastereo-isomeric propargylic alcohols: 5a (n-glycero, R) and 5b (L-glycero, S) in 70% yield and in the 33:67 ratio. Hydrogenalion of 5a and 5b over Pd/BaSO₄ gave cis-allylic alcohols 6a and 6b. Semireduction of the triple bond in 3 with tri-n-butyltin hydride afforded trans-olefin 7 which reacted with 4 yielding two diastereoisomeric trans-allylic alcohols: 8a (D-glycero, R) and 8b (L-glycero, S) in a 74% yield and a 72:28 ratio.