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Bronsted acid-promoted glycosylations of disaccharide glycal substructures of the saccharomicins.

ABSTRACT: An acid-promoted glycosylation and alkynol cycloisomerization sequence provided direct access to the 2-deoxytrisaccharide corresponding to the fucose-saccharosamine-digitoxose substructure of saccharomicin B. In the course of this work, the absolute stereochemistry of the repeating fucose-saccharosamine disaccharide of saccharomicins was also confirmed.

SUBMITTER: Balthaser BR

PROVIDER: S-EPMC2783931 | biostudies-literature | 2009 Nov

REPOSITORIES: biostudies-literature

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Brønsted acid-promoted glycosylations of disaccharide glycal substructures of the saccharomicins.

Balthaser Bradley R BR McDonald Frank E FE

Organic letters 20091101 21

An acid-promoted glycosylation and alkynol cycloisomerization sequence provided direct access to the 2-deoxytrisaccharide corresponding to the fucose-saccharosamine-digitoxose substructure of saccharomicin B. In the course of this work, the absolute stereochemistry of the repeating fucose-saccharosamine disaccharide of saccharomicins was also confirmed. ...[more]

PMID: 19780574

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Project description:Metal triflates have been utilized to catalytically facilitate numerous glycosylation reactions under mild conditions. In some methods, the metal triflate system provides stereocontrol during the glycosylation, rather than the nature of protecting groups on the substrate. Despite these advances, the true activating nature of metal triflates remains unclear. Our findings indicated that the in situ generation of trace amounts of triflic acid from metal triflates can be the active catalyst species in the glycosylation. This fact has been mentioned previously in metal triflate-catalyzed glycosylation reactions; however, a thorough study on the subject and its implications on stereoselectivity has yet to be performed. Experimental evidence from control reactions and 19F NMR spectroscopy have been obtained to confirm and quantify the triflic acid released from nickel triflate, for which it is of paramount importance in achieving a stereoselective 1,2-cis-2-amino glycosidic bond formation via a transient anomeric triflate. A putative intermediate resembling that of a glycosyl triflate has been detected using variable temperature NMR (1H and 13C) experiments. These observations, together with density functional theory calculations and a kinetic study, corroborate a mechanism involving triflic acid-catalyzed stereoselective glycosylation with N-substituted trifluoromethylbenzylideneamino protected electrophiles. Specifically, triflic acid facilitates formation of a glycosyl triflate intermediate which then undergoes isomerization from the stable ?-anomer to the more reactive ?-anomer. Subsequent SN2-like displacement of the reactive anomer by a nucleophile is highly favorable for the production of 1,2-cis-2-aminoglycosides. Although there is a previously reported work regarding glycosyl triflates, none of these reports have been confirmed to come from the counter ion of the metal center. Our work provides supporting evidence for the induction of a glycosyl triflate through the role of triflic acid in metal triflate-catalyzed glycosylation reactions.

Dataset Information

Bronsted acid-promoted glycosylations of disaccharide glycal substructures of the saccharomicins.

Publications

Brønsted acid-promoted glycosylations of disaccharide glycal substructures of the saccharomicins.

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