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

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Structure, Bonding and Reactivity of Heterocyclic Compounds

Part of the book series: Topics in Heterocyclic Chemistry ((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.

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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

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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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  1. Center for Molecular Modeling, Ghent University, Technologiepark 903, 9052, Zwijnaarde, Belgium

    Hannelore Goossens, Dietmar Hertsen, Saron Catak, Michel Waroquier & Veronique Van Speybroeck

  2. Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering, Ghent University, Coupure Links 653, 9000, Ghent, Belgium

    Karen Mollet, Matthias D’hooghe & Norbert De Kimpe

  3. Department of Chemistry, Bogaziçi University, Bebek, 34342, Istanbul, Turkey

    Saron Catak

  4. Research group of General Chemistry, Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium

    Frank De Proft & Paul Geerlings

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  1. Hannelore Goossens
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Correspondence to Veronique Van Speybroeck .

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  1. Research Group of General Chemistry, Vrije Universiteit Brussel (VUB), Brussels, Belgium

    Frank De Proft

  2. Research Group of General Chemistry, Vrije Universiteit Brussel (VUB), Brussels, Belgium

    Paul Geerlings

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Goossens, H. et al. (2014). Reactivity of Aziridinium Salts in Different Solvents Unraveled by a Combined Theoretical and Experimental Approach. In: De Proft, F., Geerlings, P. (eds) Structure, Bonding and Reactivity of Heterocyclic Compounds. Topics in Heterocyclic Chemistry, vol 38. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-45149-2_1

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