Halogen Atom Participation in Guiding the Stereochemical Outcomes of Acetal Substitution Reactions

Krystyna M. Demkiw, Wouter A. Remmerswaal, Thomas Hansen, Gijsbert A. van der Marel, Jeroen D.C. Codée, K. A. Woerpel

Research output: Contribution to journalArticlepeer-review

Abstract

Acetal substitution reactions of α-halogenated five- and six-membered rings can be highly stereoselective. Erosion of stereoselectivity occurs as nucleophilicity increases, which is consistent with additions to a halogen-stabilized oxocarbenium ion, not a three-membered-ring halonium ion. Computational investigations confirmed that the open-form oxocarbenium ions are the reactive intermediates involved. Kinetic studies suggest that hyperconjugative effects and through-space electrostatic interactions can both contribute to the stabilization of halogen-substituted oxocarbenium ions.

Original languageEnglish (US)
Article numbere202209401
JournalAngewandte Chemie - International Edition
Volume61
Issue number42
DOIs
StatePublished - Oct 17 2022

Keywords

  • Diastereoselectivity
  • Glycosylation
  • Halonium Ion
  • Hyperconjugation
  • Oxocarbenium Ion

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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