Using nucleophilic substitution reactions to understand how a remote alkyl or alkoxy substituent influences the conformation of eight-membered ring oxocarbenium ions

Stephen Chamberland, K. A. Woerpel

Research output: Contribution to journalArticle

Abstract

(Chemical Equation Presented) A remote alkoxy substituent strongly stabilizes one particular conformer of an eight-membered ring oxocarbenium ion by a through-space electrostatic effect. X-ray crystallographic analysis of a crystalline derivative proves that kinetically controlled nucleophilic substitution favors the 1,4-trans product. Nucleophilic substitution of the corresponding alkyl-substituted acetate, however, is unselective. A computational model has been developed and experimentally validated to predict the low-energy conformers of C3-, C4-, or C5-alkyl- or alkoxy-substituted eight-membered ring oxocarbenium ions.

Original languageEnglish (US)
Pages (from-to)4739-4741
Number of pages3
JournalOrganic Letters
Volume6
Issue number25
DOIs
StatePublished - Dec 9 2004

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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