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Protecting group-free glycoligation by the desulfurative rearrangement of allylic disulfides as a means of assembly of oligosaccharide mimetics.

ABSTRACT: 2-(2-Pyridyldithio-3-butenyl) glycosides react with carbohydrate-based thiols in a two-step process involving sulfenyl transfer followed by desulfurative 2,3-allylic rearrangement, promoted by either triphenylphosphine or silver nitrate, to give novel saccharide mimetics. In an alternative embodiment of the same chemistry anomeric thiols are coupled with carbohydrates derivatized in the form of 2-(2-pyridyldithio-3-butenyl) ethers. This new method of glycoligation does not require protection of hydroxyl groups and is compatible with the presence of acetamides, azides, trichloroethoxycarbamates, and thioglycosides. Variations on the general theme enable the preparation of mimetics of reducing and nonreducing oligosaccharides as well as of nonglycosidically linked systems.

SUBMITTER: Subramanian V

PROVIDER: S-EPMC3094498 | biostudies-literature | 2011 May

REPOSITORIES: biostudies-literature

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Protecting group-free glycoligation by the desulfurative rearrangement of allylic disulfides as a means of assembly of oligosaccharide mimetics.

Subramanian Venkataraman V Moumé-Pymbock Myriame M Hu Tianshun T Crich David D

The Journal of organic chemistry 20110323 10

2-(2-Pyridyldithio-3-butenyl) glycosides react with carbohydrate-based thiols in a two-step process involving sulfenyl transfer followed by desulfurative 2,3-allylic rearrangement, promoted by either triphenylphosphine or silver nitrate, to give novel saccharide mimetics. In an alternative embodiment of the same chemistry anomeric thiols are coupled with carbohydrates derivatized in the form of 2-(2-pyridyldithio-3-butenyl) ethers. This new method of glycoligation does not require protection of ...[more]

PMID: 21428425

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