PREDICTION OF THE REGIOSELECTIVITY OF THE RUTHENIUM-CATALYZED [3+2] CYCLOADDITIONS OF BENZYL AZIDE WITH INTERNAL ALKYNES USING CONCEPTUAL DFT INDICES OF REACTIVITY

Authors

  • Youcef Yousfi Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria
  • Wafaa Benchouk Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria
  • Sidi Mohamed Mekelleche Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria

DOI:

https://doi.org/10.1007/7221

Keywords:

internal alkynes, ruthenium catalysts, [3 2] cycloaddition reaction, Parr functions, regioselectivity.

Abstract

[3+2] Cycloadditions of benzyl azide with unsymmetrical internal alkynes, in the presence of pentamethylcyclopentadienyl ruthenium chloride [Cp*RuCl] complex as catalyst, leading to trisubstituted 1,2,3-triazole regioisomers are rationalized by means of DFT-based reactivity indices. The four activated azide/[Ru]/alkyne complexes have been modeled for all their possible conformers and were classified using the Maxwell–Boltzmann distribution. The local electrophilicity and nucleophilicity indices, based on Parr functions, have been calculated for the terminal sites of the benzyl azide and the carbon atoms of the internal alkynes. The calculations were performed at the B3LYP level of theory together with the LANL2DZ basis set for Ru and Cl and the standard 6-31G(d) basis set for the other atoms. The obtained results agree well with the experimental findings which stipulate that the formed cycloadducts depend strongly on the nature of substituents carried by the internal alkynes. The regioselectivity of six additional reactions of benzyl azide with other internal alkynes are also predicted.

Author Biographies

Youcef Yousfi, Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria

Tlemcen

Wafaa Benchouk, Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria

Tlemcen

Sidi Mohamed Mekelleche, Laboratory of Applied Thermodynamics and Molecular Modeling, Department of Chemistry, Faculty of Science, University of Tlemcen, BP 119, Tlemcen 13000, Algeria

Tlemcen

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Published

2023-04-11

Issue

Vol. 59 No. 3 (2023): Cycloaddition reactions: recent progress

Section

Original Papers