Determination of local effects for chloroaluminate ionic liquids on Diels-Alder reactions

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Abstract

Room temperature ionic liquids are an exciting class of solvents that have the potential to accelerate and control a vast range of reactions. The Diels-Alder reaction, paradigm in organic synthesis, highlights the advantages provided by ionic liquids as the reaction between cyclopentadiene and methyl acrylate in 1-ethyl-3-methylimidazolium tetrachloroaluminate and heptachlorodialuminate [EMIM][AlCl 4] and [EMIM][Al 2Cl 7], respectively, has been reported to react with rates over 200 times faster and endo selectivity 10 times greater than commonly used reaction conditions. Density functional theory (DFT) calculations at the B3LYP/6-311+G(2d,p) theory level have been employed to determine the origin of the reported rate accelerations. The DFT simulations find that specific hydrogen bonding between the ionic liquid cations and the dienophile at the transition state is primarily responsible, however, the rate of reaction was found to be moderated by the solvent's hydrogen bond accepting ability (anion effect). Different anion-to-cation ratios were tested and a 1:1 ratio was determined to give the best agreement with experimental observations. The computed DFT activation barriers were within reasonable agreement of the reported rates, however it is clear that a full microenvironment featuring hundreds of ions is necessary for proper computational treatment of the solvent effects delivered by the ionic liquids.

Original languageEnglish (US)
Pages (from-to)95-101
Number of pages7
JournalJournal of Molecular Graphics and Modelling
Volume28
Issue number2
DOIs
StatePublished - Sep 2009
Externally publishedYes

Fingerprint

Ionic Liquids
Diels-Alder reactions
Ionic liquids
Density functional theory
liquids
density functional theory
Anions
Cations
Hydrogen bonds
Negative ions
Positive ions
anions
Cyclopentanes
cations
acrylates
selectivity
Chemical activation
activation
Ions
hydrogen bonds

Keywords

  • Catalysis
  • Chloroaluminates
  • Density functional theory (DFT)
  • Diels-Alder reaction
  • Ionic liquids

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Computer Graphics and Computer-Aided Design
  • Materials Chemistry

Cite this

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title = "Determination of local effects for chloroaluminate ionic liquids on Diels-Alder reactions",
abstract = "Room temperature ionic liquids are an exciting class of solvents that have the potential to accelerate and control a vast range of reactions. The Diels-Alder reaction, paradigm in organic synthesis, highlights the advantages provided by ionic liquids as the reaction between cyclopentadiene and methyl acrylate in 1-ethyl-3-methylimidazolium tetrachloroaluminate and heptachlorodialuminate [EMIM][AlCl 4] and [EMIM][Al 2Cl 7], respectively, has been reported to react with rates over 200 times faster and endo selectivity 10 times greater than commonly used reaction conditions. Density functional theory (DFT) calculations at the B3LYP/6-311+G(2d,p) theory level have been employed to determine the origin of the reported rate accelerations. The DFT simulations find that specific hydrogen bonding between the ionic liquid cations and the dienophile at the transition state is primarily responsible, however, the rate of reaction was found to be moderated by the solvent's hydrogen bond accepting ability (anion effect). Different anion-to-cation ratios were tested and a 1:1 ratio was determined to give the best agreement with experimental observations. The computed DFT activation barriers were within reasonable agreement of the reported rates, however it is clear that a full microenvironment featuring hundreds of ions is necessary for proper computational treatment of the solvent effects delivered by the ionic liquids.",
keywords = "Catalysis, Chloroaluminates, Density functional theory (DFT), Diels-Alder reaction, Ionic liquids",
author = "Orlando Acevedo",
year = "2009",
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doi = "10.1016/j.jmgm.2009.04.003",
language = "English (US)",
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pages = "95--101",
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T1 - Determination of local effects for chloroaluminate ionic liquids on Diels-Alder reactions

AU - Acevedo, Orlando

PY - 2009/9

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N2 - Room temperature ionic liquids are an exciting class of solvents that have the potential to accelerate and control a vast range of reactions. The Diels-Alder reaction, paradigm in organic synthesis, highlights the advantages provided by ionic liquids as the reaction between cyclopentadiene and methyl acrylate in 1-ethyl-3-methylimidazolium tetrachloroaluminate and heptachlorodialuminate [EMIM][AlCl 4] and [EMIM][Al 2Cl 7], respectively, has been reported to react with rates over 200 times faster and endo selectivity 10 times greater than commonly used reaction conditions. Density functional theory (DFT) calculations at the B3LYP/6-311+G(2d,p) theory level have been employed to determine the origin of the reported rate accelerations. The DFT simulations find that specific hydrogen bonding between the ionic liquid cations and the dienophile at the transition state is primarily responsible, however, the rate of reaction was found to be moderated by the solvent's hydrogen bond accepting ability (anion effect). Different anion-to-cation ratios were tested and a 1:1 ratio was determined to give the best agreement with experimental observations. The computed DFT activation barriers were within reasonable agreement of the reported rates, however it is clear that a full microenvironment featuring hundreds of ions is necessary for proper computational treatment of the solvent effects delivered by the ionic liquids.

AB - Room temperature ionic liquids are an exciting class of solvents that have the potential to accelerate and control a vast range of reactions. The Diels-Alder reaction, paradigm in organic synthesis, highlights the advantages provided by ionic liquids as the reaction between cyclopentadiene and methyl acrylate in 1-ethyl-3-methylimidazolium tetrachloroaluminate and heptachlorodialuminate [EMIM][AlCl 4] and [EMIM][Al 2Cl 7], respectively, has been reported to react with rates over 200 times faster and endo selectivity 10 times greater than commonly used reaction conditions. Density functional theory (DFT) calculations at the B3LYP/6-311+G(2d,p) theory level have been employed to determine the origin of the reported rate accelerations. The DFT simulations find that specific hydrogen bonding between the ionic liquid cations and the dienophile at the transition state is primarily responsible, however, the rate of reaction was found to be moderated by the solvent's hydrogen bond accepting ability (anion effect). Different anion-to-cation ratios were tested and a 1:1 ratio was determined to give the best agreement with experimental observations. The computed DFT activation barriers were within reasonable agreement of the reported rates, however it is clear that a full microenvironment featuring hundreds of ions is necessary for proper computational treatment of the solvent effects delivered by the ionic liquids.

KW - Catalysis

KW - Chloroaluminates

KW - Density functional theory (DFT)

KW - Diels-Alder reaction

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