Effect of Protecting Groups and Solvents in Anomeric O-Alkylation of Mannopyranose1

Abstract

Anomeric O-alkylation of mannopyranoses with various protecting groups was investigated using mannose derivatives and 2,3-O-isopropylidene-l-O-trifluoro-methanesulfonyl-D-glycerol (1) as alkylating agent. Generally, in polar solvents higher α/β ratios were obtained than in nonpolar solvents. Sterically demanding protecting groups at the 6-O-position and polar solvents led to higher yields. Reactivity differences were explained by different complex formation. Based on these results mannopyranosyl-α(1-4) glucopyranosides 26 and 27 were synthesized using mannose derivatives 5 and 6 having a 6-O-(p-methoxyphenyl)diphenylmethyl group and galactosyl trifluoromethane-sulfonate 24 or nonafluorobutanesulfonate (nonaflate) 25, respectively, as alkylating agents.