Dehydrative glycosylation with activated diphenyl sulfonium reagents. Scope, mode of C(1)-hemiacetal activation, and detection of reactive glycosyl intermediates

Brian A. Garcia, David Y. Gin

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238 Scopus citations

Abstract

The development of a method for direct dehydrative glycosylations with 1-hydroxyglycosyl donors employing the reagent combination of triflic anhydride and diphenyl sulfoxide is described. The one-pot coupling method is a facile process which is applicable to a variety of carbohydrate coupling partners. Oxygen-18-labeling studies are consistent with the first step in carbohydrate activation being the formation of an anomeric oxosulfonium intermediate. This reactive glycosyl species (35) is observable in low-temperature NMR experiments when 2,3,4,6-tetra-O-methyl-D-mannopyranose is activated as the glycosyl donor. When the dehydrative glycosylation reaction is performed in the presence of the triflic acid scavenger 2-chloropyridine, NMR analysis reveals that the glycosyl oxosulfonium intermediate 35 is converted to the corresponding anomeric 2-chloropyridinium species 36.

Original languageEnglish
Pages (from-to)4269-4279
Number of pages11
JournalJournal of the American Chemical Society
Volume122
Issue number18
DOIs
StatePublished - May 10 2000

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