Divulging the various chemical reactivity of trifluoromethyl-4-vinyl-benzene as well as methyl-4-vinyl-benzene in [3+2] cycloaddition reactions

El Idrissi M., EŞME A., Hakmaoui Y., Rios-Gutierrez M., Ouled Aitouna A., Salah M., ...More

JOURNAL OF MOLECULAR GRAPHICS & MODELLING, vol.102, 2021 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 102
  • Publication Date: 2021
  • Doi Number: 10.1016/j.jmgm.2020.107760
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, Applied Science & Technology Source, BIOSIS, Biotechnology Research Abstracts, Chemical Abstracts Core, Chimica, Compendex, Computer & Applied Sciences, EMBASE, INSPEC, MEDLINE
  • Keywords: Benzonitrileoxide, MEDT, Regioselectivity, [3+2] cycloadditionreactions, DFT, ELF
  • Kocaeli University Affiliated: Yes


In the present paper, an investigation about the [3 + 2]cycloaddition (32 C A) reactions of benzonitrile oxide with 1-trifluoromethyl-4-vinyl-benzene, and with 1-methyl-4-vinyl-benzene, using the Molecular Electron Density Theory (MEDT) through DFT/B3LYP/6-311++G (d,p), is performed. A deep mechanistic study beside an accurate electronic description of different stationary points along the IRC paths of the two 32 C A reactions have performed by examining the two competitive regioisomericortho/metareaction pathways, and providing the mechanism associated with them. The presence of the CF3 group reduces the activation energy, which makes it possible to increase the experimental yield of the reaction in good agreement with the experimental results. Addition of solvent (THF) does not affected the regioselectivity of the studied reactions. Evaluation of the ELF of selected structures of the IRC related with the formation of C-O and C-C single bonds designates that these 32 C A reactions take place through a one-step, two-stage mechanism. (c) 2020 Elsevier Inc. All rights reserved.