Influence of the Structure of Polyfluorinated Alcohols on Bronsted Acidity/Hydrogen-Bond Donor Ability and Consequences on the Promoter Effect

Daniela Vuluga, Julien Legros, Benoit Crousse, Alexandra M. Z. Slawin, Christian Laurence, Pierre Nicolet, Daniele Bonnet-Delpon

Research output: Contribution to journalArticlepeer-review

86 Citations (Scopus)

Abstract

The influence of substituents on the properties of tri- and hexafluorinated alcohols derived from 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was examined. Measurements of specific solvent solute interactions revealed that H-bond donation (HBD) of fluorinated alcohols is sensitive to the steric hindrance of the OH group, whereas their Bronsted acidity is dependent only on the number of fluorine atoms. For hexafluorinated alcohols (HFAs), their association with amines characterized by X-ray diffraction showed that the balance between HBD and acidity is influenced by their structure. Moreover, the ability of HFAs to donate H-bonds is exerted in synclinal (sc), synperiplanar (sp), and also antiperiplanar (ap) conformations along the C-O bond. Comparison of the effects of fluorinated alcohols as promoting solvents in three reactions is reported. The positive correlation between rate constants and H-bonding donation ability for sulfide oxidation and imino Diels-Alder reaction brings to light the role of this property, while acidity might have a minor influence. In the third reaction, epoxide opening by piperidine, none of these properties can clearly be put forward at this stage.

Original languageEnglish
Pages (from-to)1126-1133
Number of pages8
JournalThe Journal of Organic Chemistry
Volume76
Issue number4
DOIs
Publication statusPublished - 18 Feb 2011

Keywords

  • AQUEOUS HYDROGEN-PEROXIDE
  • SELENIUM-CATALYZED OXIDATIONS
  • FLUORINATED ALCOHOLS
  • OLEFIN EPOXIDATION
  • ELECTROPHILIC PROPERTIES
  • MULTICOMPONENT REACTION
  • HOMOGENEOUS SOLUTION
  • SELECTIVE OXIDATION
  • EFFICIENT SYNTHESIS
  • TEMPLATE CATALYSIS

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