Vanadium-Catalyzed Epoxidations of Olefinic Alcohols in Liquid Carbon Dioxide

David R. Pesiri, David K. Monta, Teri Walker, William Tumas

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The selective epoxidation of olefinic alcohols with t-BuOOH in the presence of vanadium catalysts proceeds in liquid carbon dioxide with high conversions and selectivities. Rates measured in liquid CO2 for the oxovanadium(V) triisopropoxide catalyzed epoxidation of allylic and homoallylic alcohols using tert-butyl hydroperoxide are comparable to those measured in methylene chloride, toluene, and n-hexane. The reactivity of the vanadium(IV) bis(acetylacetonato) oxide catalyst in liquid CO2 was found to be substantially lower than in organic solvents, presumably due to its low solubility in C02. Highly fluorinated acac-type ligands increased the catalytic reactivity of VO(acac)2-catalyzed epoxidations by enhancing catalyst precursor solubility. Heterogeneous epoxidation reactions were also carried out in liquid CO2 using vanadium complexes supported on cation-exchange polymers.

Original languageEnglish
Pages (from-to)4916-4924
Number of pages9
JournalOrganometallics
Volume18
Issue number24
Publication statusPublished - Nov 22 1999

Fingerprint

Vanadium
epoxidation
Epoxidation
Carbon Dioxide
vanadium
carbon dioxide
alcohols
Alcohols
Liquids
liquids
catalysts
Catalysts
solubility
reactivity
Solubility
tert-Butylhydroperoxide
Methylene Chloride
Toluene
methylene
Organic solvents

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

Cite this

Pesiri, D. R., Monta, D. K., Walker, T., & Tumas, W. (1999). Vanadium-Catalyzed Epoxidations of Olefinic Alcohols in Liquid Carbon Dioxide. Organometallics, 18(24), 4916-4924.

Vanadium-Catalyzed Epoxidations of Olefinic Alcohols in Liquid Carbon Dioxide. / Pesiri, David R.; Monta, David K.; Walker, Teri; Tumas, William.

In: Organometallics, Vol. 18, No. 24, 22.11.1999, p. 4916-4924.

Research output: Contribution to journalArticle

Pesiri, DR, Monta, DK, Walker, T & Tumas, W 1999, 'Vanadium-Catalyzed Epoxidations of Olefinic Alcohols in Liquid Carbon Dioxide', Organometallics, vol. 18, no. 24, pp. 4916-4924.
Pesiri, David R. ; Monta, David K. ; Walker, Teri ; Tumas, William. / Vanadium-Catalyzed Epoxidations of Olefinic Alcohols in Liquid Carbon Dioxide. In: Organometallics. 1999 ; Vol. 18, No. 24. pp. 4916-4924.
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