1083237-11-9

Upstream product

• 1083237-08-4 phenyl 2,3,6-tri-O-benzyl-4-O-(2-carboxybenzoyl)-1-thio-β-D-galactopyranoside 
• 100-09-4 4-methoxybenzoic acid 
• 108-98-5 thiophenol 
• 100-07-2 4-methoxy-benzoyl chloride 
• 144781-45-3 phenyl 2,3,6-tri-O-benzyl-1-thio-β-D-galactopyranoside 

Relevant academic research and scientific papers

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

The synthesis and conformational analysis of a series of phenyl 2,3,6-tri-O-benzyl-β-d-thio galacto- and glucopyranosides and their 6S-deuterio isotopomers, with systematic variation of the protecting group at the 4-position, are described. For the galactopyranosides, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable shift in side chain population away from the trans,gauche conformation and in favor of the gauche,trans conformer. In the glucopyranoside series on the other hand, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable increase in the population of the trans,gauche conformer at the expense of the gauche,gauche conformer. The possible modulating effect of these conformational changes on the well-known changes in the anomeric reactivity of glycosyl donors as a function of protecting group is discussed, raising the possibility that larger changes may be observed at the transition state for glycosylation. A comparable study with a series of ethyl 2,3,4-tri-O-benzyl-β-d-thioglucopyranosides reveals that no significant influence in side chain population is observed on changing the O6 protecting group.

Does neighboring group participation by non-vicinal esters play a role in glycosylation reactions? Effective probes for the detection of bridging intermediates

(Chemical Equation Presented) Neighboring group participation in glycopyranosylation reactions is probed for esters at the 3-O-axial and -equatorial, 4-O-axial and -equatorial, and 6-O-sites of a range of donors through the use tert-butoxycarbonyl esters. The anticipated intermediate cyclic dioxanyl cation is interrupted for the axial 3-O-derivative, leading to the formation of a 1,3-O-cyclic carbonate ester, with loss of a tert-butyl cation, providing convincing evidence of participation by esters at that position. However, no evidence was found for such a fragmentation of carbonate esters at the 3-O-equatorial, 4-O-axial and -equatorial, and 6-O positions, indicating that neighboring group participation from those sites does not occur under typical glycosylation conditions. Further probes employing a 4-O-(2-carboxy)benzoate ester and a 4-O-(4-methoxybenzoate) ester, the latter in conjunction with an 18O quench designed to detect bridging intermediates, also failed to provide evidence for participation by 4-O-esters in galactopyranosylation.