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

Mohammed El Idrissi; Asli Eşme; Yassine Hakmaoui; Mar Ríos-Gutiérrez; Anas Ouled Aitouna; Mohammed Salah; Abdellah Zeroual; Luis R Domingo

doi:10.1016/j.jmgm.2020.107760

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

J Mol Graph Model. 2021 Jan:102:107760. doi: 10.1016/j.jmgm.2020.107760. Epub 2020 Sep 24.

Authors

Mohammed El Idrissi¹, Asli Eşme², Yassine Hakmaoui³, Mar Ríos-Gutiérrez⁴, Anas Ouled Aitouna⁵, Mohammed Salah⁶, Abdellah Zeroual⁷, Luis R Domingo⁴

Affiliations

¹ Molecular Modeling and Spectroscopy Research Team, Faculty of Science, ChouaïbDoukkaliUniversity, P.O. Box 20, 24000, El Jadida, Morocco; Laboratory of Chemical Processes and Applied Materials, Sultan MoulaySlimane University, FacultyPolydisciplinaryBeni-Mellal, Morocco.
² Department of Elementary Science Education Faculty of Education Kocaeli University, 41380, Umuttepe, Kocaeli, Turkey.
³ Organic and Analytical Chemistry Laboratory, Sultan MoulaySlimane University, Faculty of Science andTechnology, Beni-Mellal, BP, 523, Morocco.
⁴ Department of Organic Chemistry, University of Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain.
⁵ Molecular Modeling and Spectroscopy Research Team, Faculty of Science, ChouaïbDoukkaliUniversity, P.O. Box 20, 24000, El Jadida, Morocco.
⁶ Molecular Modeling and Spectroscopy Research Team, Faculty of Science, ChouaïbDoukkaliUniversity, P.O. Box 20, 24000, El Jadida, Morocco. Electronic address: salahmed534@gmail.com.
⁷ Molecular Modeling and Spectroscopy Research Team, Faculty of Science, ChouaïbDoukkaliUniversity, P.O. Box 20, 24000, El Jadida, Morocco. Electronic address: zeroualabdellah2@gmail.com.

PMID: 33130389
DOI: 10.1016/j.jmgm.2020.107760

Abstract

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.

Keywords: Benzonitrileoxide; DFT; ELF; MEDT; Regioselectivity; [3+2] cycloadditionreactions.

Publication types

Research Support, Non-U.S. Gov't

MeSH terms

Benzene*
Cycloaddition Reaction
Electrons*
Models, Molecular
Solvents

Substances

Solvents
Benzene