Generation of Glycosyl Radicals from Glycosyl Sulfoxides and Its Use in the Synthesis of C-linked Glycoconjugates

We here report glycosyl sulfoxides appended with an aryl iodide moiety as readily available, air and moisture stable precursors to glycosyl radicals. These glycosyl sulfoxides could be converted to glycosyl radicals by way of a rapid and efficient intramolecular radical substitution event. The use of this type of precursors enabled the synthesis of various complex C-linked glycoconjugates under mild conditions. This reaction could be performed in aqueous media and is amenable to the synthesis of glycopeptidomimetics and carbohydrate-DNA conjugates.

Automated summary

Glycosyl sulfoxides appended with an aryl iodide moiety are reported as stable precursors to glycosyl radicals, which can be converted rapidly and efficiently through intramolecular radical substitution for the synthesis of complex C-linked glycoconjugates under mild conditions, including glycopeptidomimetics and carbohydrate-DNA conjugates in aqueous media.