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Reactivity of three-membered heterocyclic rings with respect to sodium methoxide

Hannelore Goossens, Saron Catak UGent, Frank De Proft, Paul Geerlings, Michel Waroquier UGent and Veronique Van Speybroeck UGent (2011) Applications of Density Functional Theory in Chemistry and Physics, 14th International conference, Abstracts. p.44-44
abstract
Aziridines can be ‘activated’ or ‘non-activated’, depending on whether their N-substituent is an electron-withdrawing group or an electron-donating group, respectively. Activated aziridines are much more susceptible to ring opening than non-activated aziridines and epoxides are even more reactive. The difference in reactivity between activated 2-(bromomethyl)-1-tosylaziridines, non-activated 1-benzyl-2-(bromomethyl)aziridines and epibromohydrins with respect to sodium methoxide was comparatively analysed by means of DFT calculations, such as BMK, MPW1K and MPWB95 [1]. Nucleophilic substitution reactions are known to be influenced by the solvent environment. Therefore, the gas-phase results were extended towards a discrete solvent approach. The solvent effect was taken into account by inspecting the convergence behaviour of the energy of solvation in terms of a systematically increasing number of solvent molecules. To model each of the reactive profiles of the various substrates, a supermolecule model was used with five explicit methanol molecules. Solvation has significantly changed the landscape of the energy profiles, which nicely shows the necessity of taking into account explicit solvation molecules to obtain the correct reaction profiles. The barriers for direct displacement of bromide by methoxide in methanol are comparable for all three heterocyclic species under study. However, ring opening is only feasible for the epoxide and the activated aziridine and not for the non-activated aziridine.
Please use this url to cite or link to this publication:
author
organization
year
type
conference
publication status
published
subject
keyword
aziridines, DFT, nucleophiles, microsolvation
in
Applications of Density Functional Theory in Chemistry and Physics, 14th International conference, Abstracts
pages
44 - 44
conference name
14th International conference on the Applications of Density Functional Theory in Chemistry and Physics (DFT-11)
conference location
Athens, Greece
conference start
2011-08-29
conference end
2011-09-02
language
English
UGent publication?
yes
classification
C3
copyright statement
I have transferred the copyright for this publication to the publisher
id
1946466
handle
http://hdl.handle.net/1854/LU-1946466
date created
2011-11-22 12:13:17
date last changed
2016-12-19 15:37:19
@inproceedings{1946466,
  abstract     = {Aziridines can be {\textquoteleft}activated{\textquoteright} or {\textquoteleft}non-activated{\textquoteright}, depending on whether their N-substituent is an electron-withdrawing group or an electron-donating group, respectively. Activated aziridines are much more susceptible to ring opening than non-activated aziridines and epoxides are even more reactive. The difference in reactivity between activated 2-(bromomethyl)-1-tosylaziridines, non-activated 1-benzyl-2-(bromomethyl)aziridines and epibromohydrins with respect to sodium methoxide was comparatively analysed by means of DFT calculations, such as BMK, MPW1K and MPWB95 [1].
Nucleophilic substitution reactions are known to be influenced by the solvent environment. Therefore, the gas-phase results were extended towards a discrete solvent approach. The solvent effect was taken into account by inspecting the convergence behaviour of the energy of solvation in terms of a systematically increasing number of solvent molecules. To model each of the reactive profiles of the various substrates, a supermolecule model was used with five explicit methanol molecules. Solvation has significantly changed the landscape of the  energy profiles, which nicely shows the necessity of taking into account explicit solvation molecules to obtain the correct reaction profiles.
The barriers for direct displacement of bromide by methoxide in methanol are comparable for all three heterocyclic species under study. However, ring opening is only feasible for the epoxide and the activated aziridine and not for the non-activated aziridine.},
  author       = {Goossens, Hannelore and Catak, Saron and De Proft, Frank and Geerlings, Paul and Waroquier, Michel and Van Speybroeck, Veronique},
  booktitle    = {Applications of Density Functional Theory in Chemistry and Physics, 14th International conference, Abstracts},
  keyword      = {aziridines,DFT,nucleophiles,microsolvation},
  language     = {eng},
  location     = {Athens, Greece},
  pages        = {44--44},
  title        = {Reactivity of three-membered heterocyclic rings with respect to sodium methoxide},
  year         = {2011},
}

Chicago
Goossens, Hannelore, Saron Catak, Frank De Proft, Paul Geerlings, Michel Waroquier, and Veronique Van Speybroeck. 2011. “Reactivity of Three-membered Heterocyclic Rings with Respect to Sodium Methoxide.” In Applications of Density Functional Theory in Chemistry and Physics, 14th International Conference, Abstracts, 44–44.
APA
Goossens, Hannelore, Catak, S., De Proft, F., Geerlings, P., Waroquier, M., & Van Speybroeck, V. (2011). Reactivity of three-membered heterocyclic rings with respect to sodium methoxide. Applications of Density Functional Theory in Chemistry and Physics, 14th International conference, Abstracts (pp. 44–44). Presented at the 14th International conference on the Applications of Density Functional Theory in Chemistry and Physics (DFT-11).
Vancouver
1.
Goossens H, Catak S, De Proft F, Geerlings P, Waroquier M, Van Speybroeck V. Reactivity of three-membered heterocyclic rings with respect to sodium methoxide. Applications of Density Functional Theory in Chemistry and Physics, 14th International conference, Abstracts. 2011. p. 44–44.
MLA
Goossens, Hannelore, Saron Catak, Frank De Proft, et al. “Reactivity of Three-membered Heterocyclic Rings with Respect to Sodium Methoxide.” Applications of Density Functional Theory in Chemistry and Physics, 14th International Conference, Abstracts. 2011. 44–44. Print.