Influence of 3‐Thio Substituents on Benzylidene‐Directed Mannosylation. Isolation of a Bridged Pyridinium Ion and Effects of 3‐O‐Picolyl and 3‐S‐Picolyl Esters

The influence on glycosyl selectivity of substituting oxygen for sulfur at the 3-position of 4,6-O-benzylidene-protected mannopyranosyl thioglycosides is reported and varies considerably according to the protecting group employed at the 3-position. The substitution of a thioether at the 3-position for the more usual 3-O-benzyl ether results in a significant loss of selectivity. The installation of a 3-S-picolinyl thioether results in a complex reaction mixture, from which a stable seven-membered bridged bicyclic pyridinium ion is isolated, while the corresponding 3-O-picolinyl ether affords a highly α-selective coupling reaction. A 3-O-picolyl ester provides excellent β-selectivity, while the analogous 3-S-picolyl thioester gives a highly α-selective reaction. The best β-selectivity is seen with a 3-deoxy-3-(2-pyridinyldisulfanyl) system. These observations are discussed in terms of the influence of the various substituents on the central glycosyl triflate - ion pair equilibrium.