A study on the influence of the structure of the glycosyl acceptors on the stereochemistry of the glycosylation reactions with 2-azido-2-deoxy-hexopyranosyl trichloroacetimidates.
The stereochemical outcome of glycosylations with 2-azido-2-deoxy-D-gluco- and D-galactopyranosyl trichloroacetimidates as glycosyl donors has been investigated by using a series of chiro-inositol derivatives as glycosyl acceptors. The influence of the absolute configuration, the conformation and the conformational flexibility of the glycosyl acceptor has been studied by using different glycosyl donors under similar pre-established experimental conditions. Although the structure of the acceptor may play a role in governing the stereochemistry of these glycosylations, the results show that, in general terms, the relative influence of these factors is difficult to evaluate. For a given set of experimental conditions, the stereochemical course of these glycosylations depends on structural features of both glycosyl donor and glycosyl acceptor. It is a balance of these factors, where the structure of the glycosyl donor always plays a major role, which determines the stereochemistry of the coupling reaction. Therefore, the examples reported in the literature in which the structure of the glycosyl acceptor appears to be crucial in determining the stereochemistry of the reaction constitute particularly favorable cases which do not presently allow any further generalization.
Cid
M Belén
MB
Departamento de Química Orgánica, Universidad Autónoma de Madrid, 28049 Cantoblanco, Spain. belen.cid@uam.es
Alfonso
Francisco
F
Martín-Lomas
Manuel
M
D001386:Azides / Q000138:chemical synthesis* / Q000737:chemistry*; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D062845:Chloroacetates; D006031:Glycosylation; D007294:Inositol / Q000031:analogs & derivatives / Q000138:chemical synthesis* / Q000737:chemistry*; D008969:Molecular Sequence Data; D013237:Stereoisomerism; D014238:Trichloroacetic Acid / Q000138:chemical synthesis* / Q000737:chemistry*
D001386:Azides; D062845:Chloroacetates; D007294:Inositol; D014238:Trichloroacetic Acid