C-glycosylation reactions of sulfur-substituted glycosyl donors: Evidence against the role of neighboring-group participation

Matthew G. Beaver, Susan B. Billings, K. A. Woerpel

Research output: Contribution to journalArticlepeer-review

Abstract

Nucleophilic substitution reactions of C-4 sulfur-substituted tetrahydropyran acetals revealed that neighboring-group participation does not control product formation. Spectroscopic evidence for the formation of an intermediate sulfonium ion is provided, as are data from nucleophilic substitution reactions demonstrating that products are formed from oxocarbenium ion intermediates. The selectivity was not sensitive to solvent or to which Lewis acid was employed. The identity of the heteroatom at the C-4 position also did not significantly impact diastereoselectivity. Consequently, neighboring-group participation was not responsible for the formation of either the major or the minor products. These studies implicate a Curtin-Hammett kinetic scenario in which the formation of a low-energy intermediate does not necessitate its involvement in the product-forming pathway.

Original languageEnglish (US)
Pages (from-to)2082-2086
Number of pages5
JournalJournal of the American Chemical Society
Volume130
Issue number6
DOIs
StatePublished - Feb 13 2008

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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