Mechanistic insights into the triazolylidene-catalysed Stetter and benzoin reactions: role of the N-aryl substituent

Christopher J. Collett, Richard S. Massey, Oliver R. Maguire, Andrei S. Batsanov, AnnMarie C. O'Donoghue*, Andrew D. Smith

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

100 Citations (Scopus)
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Abstract

The in situ observation, isolation and reversible formation of intermediate 3-(hydroxybenzyl) azolium salts derived from NHC addition to a range of substituted benzaldehydes is probed. Equilibrium constants for the formation of these 3-(hydroxybenzyl) azolium salts, as well as rate constants of hydrogen-deuterium exchange (k(ex)) at C(alpha) of these intermediates for a range of N-aryl triazolinylidenes is reported. These combined studies give insight into the preference of N-pentafluorophenyl NHCs to participate in benzoin and Stetter reaction processes.

Original languageEnglish
Pages (from-to)1514-1522
Number of pages9
JournalChemical Science
Volume4
Issue number4
Early online date4 Jan 2013
DOIs
Publication statusPublished - 2013

Keywords

  • Heterocyclic carbene
  • Thiazolium salts
  • Michael addition
  • Triazolium salts
  • Umpolung reaction
  • Nucleophilic carbenes
  • Breslow intermediate
  • Alpha,beta-unsaturated aldehydes
  • Thiamine action
  • Homoenolate equivalents

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