Structure, Bonding and Reactivity of Heterocyclic Compounds

Editors: Frank De Proft, Paul Geerlings

Publisher: Springer Berlin Heidelberg

Book Series : Topics in Heterocyclic Chemistry

Part of: Springer Professional "Wirtschaft+Technik" , Springer Professional "Technik" , Springer Professional "Wirtschaft"

About this book

The series Topics in Heterocyclic Chemistry presents critical reviews on present and future trends in the research of heterocyclic compounds. Overall the scope is to cover topics dealing with all areas within heterocyclic chemistry, both experimental and theoretical, of interest to the general heterocyclic chemistry community. The series consists of topic related volumes edited by renowned editors with contributions of experts in the field.

Frontmatter

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

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.

Hannelore Goossens, Dietmar Hertsen, Karen Mollet, Saron Catak, Matthias D’hooghe, Frank De Proft, Paul Geerlings, Norbert De Kimpe, Michel Waroquier, Veronique Van Speybroeck

Characterization of the Chemical Reactivity and Selectivity of DNA Bases Through the Use of DFT-Based Descriptors

Abstract

In this chapter, the use of conceptual DFT descriptors for understanding the occurrence and likely mechanisms of formation of DNA lesions is reviewed. After a synthetic presentation of the principal DFT-based descriptors, the global reactivity and selectivity of DNA bases are investigated from global and local descriptors. Then, the formation of several DNA lesions is studied including cytosine compound deamination, intra-strand DNA cross-links, and pyrimidine dimer photoproducts. It appears from the use of the global and local DFT-based descriptors that most of the experimental facts can be theoretically rationalized.

Vanessa Labet, Christophe Morell, Vincent Tognetti, Olga A. Syzgantseva, Laurent Joubert, Nelly Jorge, André Grand, Jean Cadet

Characterising Heterocyclic Rings Through Quantum Chemical Topology

Abstract

In this chapter, ring structures are characterised through their calculated properties within the theory of quantum chemical topology (QCT). QCT properties of the atoms within a ring can predict the properties at a special point, a so-called ring critical point (RCP). Both the RCP properties and the atomic properties according to QCT successfully distinguish between different ring structures. There are four features of a ring that are responsible for its ring atom properties: (i) the number of heteroatoms within the ring, (ii) the heteroatom’s element, (iii) the ring substituent, and (iv) the substituent site. Interestingly, the four features affect the ring’s properties independently. Therefore, a change in a heteroatom’s element will always affect the ring’s properties the same amount, irrespective of other ring features. This is called ring characteristic orthogonality. For substituent types, it is the atom of the substituent connecting the substituent to the ring that dominates the effect on the ring, rather than the entire substituent itself. Using these relationships between ring features and QCT properties opens up the possibility of improving ring structures in areas such as drug design.

Mark Z. Griffiths, Paul L. A. Popelier

Valence Bond Theory in Heterocyclic Chemistry

Abstract

This chapter deals with the application of valence bond theory in heterocyclic chemistry. A short introduction to the different valence bond methods is given, followed by illustrative results obtained by valence bond calculations. The illustrations show the applicability of the valence bond theory to obtain detailed information on the electronic structure of molecules in terms of chemical concepts.

Zahid Rashid, Ria Broer, Joop H. van Lenthe, Remco W. A. Havenith

Aromaticity of Organic and Inorganic Heterocycles

Abstract

Heteroaromatic rings are present in many organic molecules. They can be found as part of the core of drugs or agrochemicals and in many important biochemical molecules. The last three centuries have brought important advances in heteroaromatic chemistry. Indeed, the first organic molecules with heteroaromatic rings were already synthesized in the middle of the nineteenth century. Then, the twentieth century witnessed the first inorganic heteroaromatic compound produced in the laboratory. And at the beginning of the present century, the first all-metal heteroaromatic cluster was detected. Here, we discuss the aromaticity of some of these heteroaromatic compounds using different descriptors of aromaticity, with special emphasis in those measures based on electron delocalization properties of the aromatic rings.

Ferran Feixas, Jordi Poater, Eduard Matito, Miquel Solà

Chemical Bonding and Aromaticity in Poly-heterocyclic Compounds

Abstract

This chapter is devoted to a theoretical analysis of the nature of chemical bonding, and in particular the aromaticity, of some intriguing poly-heterocyclic compounds which have recently been synthesized including the sulflowers and derivatives. The novel concept of disk aromaticity proposed as a measure of the aromatic character of planar double-ring boron clusters is applied in this context for poly-heterocyclic compounds.

Truong Ba Tai, Vu Thi Thu Huong, Minh Tho Nguyen

Backmatter

Title: Structure, Bonding and Reactivity of Heterocyclic Compounds
Editors: Frank De Proft
Paul Geerlings
Publisher: Springer Berlin Heidelberg
Electronic ISBN: 978-3-642-45149-2
Print ISBN: 978-3-642-45148-5
DOI: https://doi.org/10.1007/978-3-642-45149-2

Springer Professional

Structure, Bonding and Reactivity of Heterocyclic Compounds

About this book

Table of Contents

Frontmatter

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

Characterization of the Chemical Reactivity and Selectivity of DNA Bases Through the Use of DFT-Based Descriptors

Characterising Heterocyclic Rings Through Quantum Chemical Topology

Valence Bond Theory in Heterocyclic Chemistry

Aromaticity of Organic and Inorganic Heterocycles

Chemical Bonding and Aromaticity in Poly-heterocyclic Compounds

Backmatter

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