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Reactivity of Aziridinium Salts in Different Solvents Unraveled by a Combined Theoretical and Experimental Approach

  • Hannelore Goossens
  • Dietmar Hertsen
  • Karen Mollet
  • Saron Catak
  • Matthias D’hooghe
  • Frank De Proft
  • Paul Geerlings
  • Norbert De Kimpe
  • Michel Waroquier
  • Veronique Van SpeybroeckEmail author
Chapter
Part of the Topics in Heterocyclic Chemistry book series (TOPICS, volume 38)

Abstract

This chapter focuses on the importance of aziridinium ions as intermediates in organic chemistry. The principal aim is to gain insight into the factors to take into account for the selective synthesis of a variety of functionalized amines via aziridinium salts, such as the nature of the aziridinium ion (ring strain and N- and C-substituents of the aziridine ring), the nucleophile, and the solvent environment. Molecular modeling is used to investigate kinetics, electrostatics, and frontier molecular orbitals of reactions involving intermediate aziridinium ions, such as the nucleophilic ring opening of aziridines, the ring expansion of nitrogen heterocycles, and the ene reactions with triazolinedione.

Keywords

Aziridinium ions DFT Ring strain Regioselectivity Solvation 

Abbreviations

AI

Aziridinium imide intermediate

CM3

Charge model 3

CSE

Conventional strain energy

CSG

Gibbs free coordination solvation energy

DFT

Density functional theory

Hirshfeld-I

Iterative Hirshfeld

LG

Leaving group

NPA

Natural population analysis

OI

Open intermediate

PM3

Semi-empirical parameterized model number 3

QM/MM

Quantum mechanics/molecular mechanics

TAD

Triazolinedione

TSabs

Transition state for proton abstraction

TSadd

Transition state for addition

TSiso

Transition state for isomerization

Notes

Acknowledgments

This work was supported by the Research Foundation-Flanders (FWO-Vlaanderen), the Research Board of Ghent University (BOF-GOA), and the IAP-BELSPO program in the frame of IAP 7/05. Computational resources and services used in this work were provided by Ghent University.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  • Hannelore Goossens
    • 1
  • Dietmar Hertsen
    • 1
  • Karen Mollet
    • 2
  • Saron Catak
    • 1
    • 3
  • Matthias D’hooghe
    • 2
  • Frank De Proft
    • 4
  • Paul Geerlings
    • 4
  • Norbert De Kimpe
    • 2
  • Michel Waroquier
    • 1
  • Veronique Van Speybroeck
    • 1
    Email author
  1. 1.Center for Molecular ModelingGhent UniversityZwijnaardeBelgium
  2. 2.Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience EngineeringGhent UniversityGhentBelgium
  3. 3.Department of ChemistryBogaziçi UniversityIstanbulTurkey
  4. 4.Research group of General ChemistryVrije Universiteit Brussel (VUB)BrusselsBelgium

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