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\begin{document}

\title{Understanding the influence of the trifluoromethyl group on the chemo-,
regio-, and stereoselectivity of {[}3+2{]}-cycloadditions of
thiocarbonyl S-methanides with \selectlanguage{greek}α,β-\selectlanguage{english}unsaturated ketones. A molecular
electron density theory study\selectlanguage{english}}



\author[1]{Lakhdar Benhamed}%
\author[1]{Sidi Mohamed Mekelleche}%
\author[1]{Wafaa Benchouk}%
\author[1]{Imad Eddine  Charif}%
\author[2]{Mar  Ríos-Gutiérrez}%
\author[3]{Luis Domingo}%
\affil[1]{Abou Bakr Belkaid University Tlemcen Faculty of Sciences}%
\affil[2]{Universitat de Valencia Facultat de Quimica}%
\affil[3]{Universidad de Valencia}%


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  \date{June 01, 2024}


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\begin{abstract}
Experimentally (G. Mlosto\selectlanguage{polish}ń \selectlanguage{english}et al., J. Fluor. Chem. 190 (2016) 56--60),
it has been found that the type of the obtained cycloadduct of the
{[}3+2{]} cycloaddition (32CA) reaction of thiocarbonyl S-methanides
with \selectlanguage{greek}α,β-\selectlanguage{english}unsaturated ketones depends strongly on the location of the
trifluoromethyl group. In the case of enones containing the CF3CH=CH
moiety, the 32CA reaction occurs chemo- and regioselectively onto the
C=C double bond giving trifluoromethylated tetrahydrothiophene
derivatives. On the other hand, enones containing the CF3--C=O fragment
react as carbonyl heteroethylenes leading to trifluoromethylated
1,3-oxathiolanes also in a chemo- and regioselective manner. Our aim in
the present work is to perform a theoretical study of the all chemo-,
regio-, and stereo-isomeric reaction paths of these 32CA reactions
within the Molecular Electron Density Theory. Activation Gibbs free
energies, calculated at the B3LYP/6-311G(d,p) level in tetrahydrofurane
at -40\selectlanguage{ngerman}°C, show that the ortho/endo reaction path giving the
trifluoromethylated tetrahydrothiophene is more favoured, while the
meta/endo reaction path leading to trifluoromethylated 1,3-oxathiolanes
is more preferred in total agreement with experimental findings. The low
activation barriers in combination of the Electron Localization Function
topological analysis of the most relevant points along the Intrinsic
Reaction Coordinate reveals the pseudomonoradical character of the
studied 32CA reactions.%
\end{abstract}\selectlanguage{ngerman}%



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