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Systematic study of halide-induced ring opening of 2-substituted aziridinium salts and theoretical rationalization of the reaction pathways

Matthias D'hooghe UGent, Saron Catak UGent, Sonja Stanković UGent, Michel Waroquier UGent, Yongeun Kim, Hyun-Joon Ha, Veronique Van Speybroeck UGent and Norbert De Kimpe UGent (2010) EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. 2010(25). p.4920-4931
abstract
The ring-opening reactions of 2-alkyl-substituted 1,1-bis(arylmethyl)- and 1-methyl-1-(1-phenylethyl)aziridinium salts with fluoride, chloride, bromide and iodide in acetonitrile have been evaluated for the first time in a systematic way. The reactions with fluoride afforded regioisomeric mixtures of primary and secondary fluorides, whereas secondary β-chloro, β-bromo and β-iodo amines were obtained as the sole reaction products from the corresponding halides by regiospecific ring opening at the substituted position. Both experimental and computational results revealed that the reaction outcomes in the cases of chloride, bromide and iodide were dictated by product stability through thermodynamic control involving rearrangement of the initially formed primary halides to the more stable secondary halides. The ring opening of the same aziridinium salts with fluoride, however, was shown to be mediated by steric interactions (kinetic control), with the corresponding primary β-fluoro amines being obtained as the main reaction products. Only for 2-acylaziridinium ions was the reaction outcome shown to be under full substrate control, affording secondary β-fluoro, β-chloro, β-bromo and β-iodo amines through exclusive attack at the activated α-carbonyl carbon atom.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
Reaction mechanisms, Density functional calculations, Nitrogen heterocycles, Aziridines, Regioselectivity, Halides, CONTINUUM SOLVENT CALCULATIONS, BETA-AMINO ACIDS, CHIRAL AZIRIDINES, SYNTHETIC APPLICATIONS, SOLVATION MODELS, FLUORO AMINES, ASPARTIC-ACID, ENERGY, 2-(CYANOMETHYL)AZIRIDINES, REGIOSELECTIVITY
journal title
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY
Eur. J. Org. Chem.
volume
2010
issue
25
pages
4920 - 4931
Web of Science type
Article
Web of Science id
000282110500017
JCR category
CHEMISTRY, ORGANIC
JCR impact factor
3.206 (2010)
JCR rank
13/56 (2010)
JCR quartile
1 (2010)
ISSN
1434-193X
DOI
10.1002/ejoc.201000486
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1028905
handle
http://hdl.handle.net/1854/LU-1028905
date created
2010-08-25 15:18:54
date last changed
2013-09-17 10:47:10
@article{1028905,
  abstract     = {The ring-opening reactions of 2-alkyl-substituted 1,1-bis(arylmethyl)- and 1-methyl-1-(1-phenylethyl)aziridinium salts with fluoride, chloride, bromide and iodide in acetonitrile have been evaluated for the first time in a systematic way. The reactions with fluoride afforded regioisomeric mixtures of primary and secondary fluorides, whereas secondary \ensuremath{\beta}-chloro, \ensuremath{\beta}-bromo and \ensuremath{\beta}-iodo amines were obtained as the sole reaction products from the corresponding halides by regiospecific ring opening at the substituted position. Both experimental and computational results revealed that the reaction outcomes in the cases of chloride, bromide and iodide were dictated by product stability through thermodynamic control involving rearrangement of the initially formed primary halides to the more stable secondary halides. The ring opening of the same aziridinium salts with fluoride, however, was shown to be mediated by steric interactions (kinetic control), with the corresponding primary \ensuremath{\beta}-fluoro amines being obtained as the main reaction products. Only for 2-acylaziridinium ions was the reaction outcome shown to be under full substrate control, affording secondary \ensuremath{\beta}-fluoro, \ensuremath{\beta}-chloro, \ensuremath{\beta}-bromo and \ensuremath{\beta}-iodo amines through exclusive attack at the activated \ensuremath{\alpha}-carbonyl carbon atom.},
  author       = {D'hooghe, Matthias and Catak, Saron and Stankovi\'{c}, Sonja and Waroquier, Michel and Kim, Yongeun and Ha, Hyun-Joon and Van Speybroeck, Veronique and De Kimpe, Norbert},
  issn         = {1434-193X},
  journal      = {EUROPEAN JOURNAL OF ORGANIC CHEMISTRY},
  keyword      = {Reaction mechanisms,Density functional calculations,Nitrogen heterocycles,Aziridines,Regioselectivity,Halides,CONTINUUM SOLVENT CALCULATIONS,BETA-AMINO ACIDS,CHIRAL AZIRIDINES,SYNTHETIC APPLICATIONS,SOLVATION MODELS,FLUORO AMINES,ASPARTIC-ACID,ENERGY,2-(CYANOMETHYL)AZIRIDINES,REGIOSELECTIVITY},
  language     = {eng},
  number       = {25},
  pages        = {4920--4931},
  title        = {Systematic study of halide-induced ring opening of 2-substituted aziridinium salts and theoretical rationalization of the reaction pathways},
  url          = {http://dx.doi.org/10.1002/ejoc.201000486},
  volume       = {2010},
  year         = {2010},
}

Chicago
D’hooghe, Matthias, Saron Catak, Sonja Stanković, Michel Waroquier, Yongeun Kim, Hyun-Joon Ha, Veronique Van Speybroeck, and Norbert De Kimpe. 2010. “Systematic Study of Halide-induced Ring Opening of 2-substituted Aziridinium Salts and Theoretical Rationalization of the Reaction Pathways.” European Journal of Organic Chemistry 2010 (25): 4920–4931.
APA
D’hooghe, M., Catak, S., Stanković, S., Waroquier, M., Kim, Y., Ha, H.-J., Van Speybroeck, V., et al. (2010). Systematic study of halide-induced ring opening of 2-substituted aziridinium salts and theoretical rationalization of the reaction pathways. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2010(25), 4920–4931.
Vancouver
1.
D’hooghe M, Catak S, Stanković S, Waroquier M, Kim Y, Ha H-J, et al. Systematic study of halide-induced ring opening of 2-substituted aziridinium salts and theoretical rationalization of the reaction pathways. EUROPEAN JOURNAL OF ORGANIC CHEMISTRY. 2010;2010(25):4920–31.
MLA
D’hooghe, Matthias, Saron Catak, Sonja Stanković, et al. “Systematic Study of Halide-induced Ring Opening of 2-substituted Aziridinium Salts and Theoretical Rationalization of the Reaction Pathways.” EUROPEAN JOURNAL OF ORGANIC CHEMISTRY 2010.25 (2010): 4920–4931. Print.