No abstract

Radical halogenation-mediated glycosylation using allyl glycosides as donors and as acceptors emerges to be an efficient and hither-to unknown glycosylation method, adhering to the concept of the latent-active methodology. Several di- and trisaccharides that possess the allyl moiety at their reducing end are prepared through this new glycosylation methodology.

Chemical glycosylations occupy a central importance to synthesize tailor-made oligo- and polysaccharides of functional importance. Generation of the oxocarbenium ion or the glycosyl cation is the method of choice in order to form the glycosidic bond interconnecting a glycosyl moiety with a glycosyl/aglycosyl moiety. A number of elegant methods have been devised that allow the glycosyl cation formation in a fairly stream-lined manner to a large extent. The latent-active method provides a powerful approach in the protecting group controlled glycosylations. In this context, allyl glycosides have been developed to meet the requirement of latent-active reactivities under appropriate glycosylation conditions. Radical halogenation provides a newer route of activation of allyl glycosides to an activated allylic glycoside. Such an allylic halide activation subjects the glycoside reactive under acid catalysis, leading to the conversion to a glycosyl cation and subsequent glycosylation with a number of acceptors. The complete anomeric selectivity favoring the 1,2-trans-anomeric glycosides points to the possibility of a preferred conformation of the glycosyl cation. This article discusses about advancements in the selectivity of glycosylations, followed by delineating the allylic halogenation of allyl glycoside as a glycosylation method and demonstrates synthesis of a repertoire of di- and trisaccharides, including xylosides, with varied protecting groups.

Allylic bromination of allyl glycosides is conducted using NBS/AIBN reagents in (EtO)2CO and PhCF3 solutions, free from CCl4 as a solvent. The activated mixed halo-allyl glycosides lead to glycosylations, mediated...

No abstract