Participation of Alkoxy Groups in Reactions of Acetals: Violation of the Reactivity/Selectivity Principle in a Curtin-Hammett Kinetic Scenario

Angie Garcia, Jillian R. Sanzone, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

Nucleophilic substitution reactions of acetals having benzyloxy groups four carbon atoms away can be highly diastereoselective. The selectivity in several cases increased as the reactivity of the nucleophile increased, in violation of the reactivity/selectivity principle. The increase in selectivity with reactivity suggests that multiple conformational isomers of reactive intermediates can give rise to the products.

Original languageEnglish (US)
Pages (from-to)12087-12090
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number41
DOIs
StatePublished - Oct 1 2015

Fingerprint

Acetals
Nucleophiles
Isomers
Substitution reactions
Carbon
Atoms
Kinetics
alkoxyl radical

Keywords

  • allylic compounds
  • carbocations
  • nucleophilic substitution
  • synthetic methods
  • through-space interactions

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis

Cite this

Participation of Alkoxy Groups in Reactions of Acetals : Violation of the Reactivity/Selectivity Principle in a Curtin-Hammett Kinetic Scenario. / Garcia, Angie; Sanzone, Jillian R.; Woerpel, Keith.

In: Angewandte Chemie - International Edition, Vol. 54, No. 41, 01.10.2015, p. 12087-12090.

Research output: Contribution to journalArticle

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