Original scientific paper

https://doi.org/10.5562/cca3570

Computational Study of Electronic Influence of Guanidine Substitution on Diels-Alder Reactions of Heterocyclic Dienes

Ivana Antol ; Laboratory for physical organic chemistry, Division of organic chemistry and biochemistry, Ruđer Bošković Institute, Zagreb, Croatia
Luka Barešić ; Laboratory for physical organic chemistry, Division of organic chemistry and biochemistry, Ruđer Bošković Institute, Zagreb, Croatia
Zoran Glasovac ; Laboratory for physical organic chemistry, Division of organic chemistry and biochemistry, Ruđer Bošković Institute, Zagreb, Croatia
Davor Margetić ; Laboratory for physical organic chemistry, Division of organic chemistry and biochemistry, Ruđer Bošković Institute, Zagreb, Croatia

Abstract

Quantum-chemical calculations of cycloaddition properties of cyclic heterodienes substituted with guanidine functionality were carried out. Molecular and electronic structures of series of dienes (pyrrole, furan, thiophene, isoindole and 1,3-butadiene) were calculated and reactivity order established on the basis of FMO theory. Transition state calculations of model [4+2] cycloaddition reaction with acetylene indicate that guanidine substitution influences reaction barriers in moderate extent (up to ~4 kcal mol–1). The substitution position plays an important role on the sign and magnitude of the effect and protonation of nitrogen possessing substituents increases reactivity of dienes.

This work is licensed under a Creative Commons Attribution 4.0 International License.

Keywords

heterocyclic chemistry; cycloaddition reactions; guanidines; organic chemistry; calculations

Hrčak ID:

227083

URI

https://hrcak.srce.hr/227083

Publication date:

29.7.2019.

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