Reactions of Sugar Chlorosulfates: Part V. The Synthesis of Chlorodeoxy Sugars

The reaction of sulfuryl chloride with reducing sugars and their methyl glycopyranosides was shown to produce fully substituted pyranose derivatives containing both chlorodeoxy and chlorosulfate ester groups. It was demonstrated that the chlorodeoxy groups were formed by nucleophilic displacement (SN2) by chloride ion of specific reactive chlorosulfate groups in fully chlorosulfated intermediates. The degree of chloro-substitution was shown to be determined by both steric and electronic effects in the individual pyranose derivatives.