Fine-tuning the nucleophilic reactivities of boron ate complexes derived from aryl and heteroaryl boronic esters

Guillaume Berionni, Artem I. Leonov, Peter Mayer, Armin R. Ofial, Herbert Mayr

Research output: Contribution to journalArticlepeer-review

Abstract

Boron ate complexes derived from thienyl and furyl boronic esters and aryllithium compounds have been isolated and characterized by X-ray crystallography. Products and mechanisms of their reactions with carbenium and iminium ions have been analyzed. Kinetics of these reactions were monitored by UV/Vis spectroscopy, and the influence of the aryl substituents, the diol ligands (pinacol, ethylene glycol, neopentyl glycol, catechol), and the counterions on the nucleophilic reactivity of the boron ate complexes were examined. A Hammett correlation confirmed the polar nature of their reactions with benzhydrylium ions, and the correlation lgk(20°C) = sN(E + N) was employed to determine the nucleophilicities of the boron ate complexes and to compare them with those of other borates and boronates. The neopentyl and ethylene glycol derivatives were found to be 104times more reactive than the pinacol and catechol derivatives.

Original languageEnglish
Pages (from-to)2780-2783
Number of pages4
JournalAngewandte Chemie - International Edition
Volume54
Issue number9
DOIs
Publication statusPublished - 23 Feb 2015
Externally publishedYes

Keywords

  • Arenes
  • Boron compounds
  • Kinetics
  • Linear free energy relationships
  • Nucleophilicity

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