Fluorinated alcohols enable olefin epoxidation by H2O2: Template catalysis

Samuël P. De Visser, Jose Kaneti, Ronny Neumann, Sason Shaik

Research output: Contribution to journalArticle

72 Citations (Scopus)

Abstract

Experimental observations show that direct olefin epoxidation by H2O2, which is extremely sluggish otherwise, occurs in fluorinated alcohol (RfOH) solutions under mild conditions requiring no additional catalysts. Theoretical calculations of ethene and propene epoxidation by H2O2 in the gas phase and in the presence of methanol and of two fluorinated alcohols, presented in this paper, show that the fluoro alcohol itself acts as a catalyst for the reaction by providing a template that stabilizes specifically the transition state (TS) of the reaction. Thus, much like an enzyme, the fluoro alcohol provides a complementary charge template that leads to the reduction of the barrier by 5-8 kcal mol-1. Additionally, the fluoro alcohol template keeps the departing OH and hydroxyalkenyl moieties in close proximity and, by polarizing them, facilitates the hydrogen migration from the latter to form water and the epoxide product. The reduced activation energy and structural confinement of the TS over the fluoro alcohol template render the epoxidation reaction observable under mild synthetic conditions.

Original languageEnglish
Pages (from-to)2903-2912
Number of pages10
JournalJournal of Organic Chemistry
Volume68
Issue number7
DOIs
Publication statusPublished - Apr 4 2003

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Epoxidation
Alkenes
Catalysis
Alcohols
Catalysts
Epoxy Compounds
Methanol
Hydrogen
Activation energy
Gases
Water
Enzymes

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Fluorinated alcohols enable olefin epoxidation by H2O2 : Template catalysis. / De Visser, Samuël P.; Kaneti, Jose; Neumann, Ronny; Shaik, Sason.

In: Journal of Organic Chemistry, Vol. 68, No. 7, 04.04.2003, p. 2903-2912.

Research output: Contribution to journalArticle

De Visser, Samuël P. ; Kaneti, Jose ; Neumann, Ronny ; Shaik, Sason. / Fluorinated alcohols enable olefin epoxidation by H2O2 : Template catalysis. In: Journal of Organic Chemistry. 2003 ; Vol. 68, No. 7. pp. 2903-2912.
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