caa a22 4500 605513252 CHVBK 20210128100659.0 cr unu---uuuuu 210128e20150501xx s 000 0 eng 10.1007/s00894-015-2658-5 doi (NATIONALLICENCE)springer-10.1007/s00894-015-2658-5 Understanding the role of the trifluoromethyl group in reactivity and regioselectivity in [3+2] cycloaddition reactions of enol acetates with nitrones. A DFT study [Elektronische Daten] [Hatem Layeb, Abdelmalek Nacereddine, Abdelhafid Djerourou, Mar Ríos-Gutiérrez, Luis Domingo] The mechanism of the [3+2] cycloaddition (32CA) reaction of C-phenyl-N-methylnitrone with ethyl trifluoroacetoacetate has been theoretically studied at the MPWB1K/6-311G(d,p) level. This 32CA reaction, in which the enol form of the β-keto ester participates as the ethylene component, takes place with complete ortho regioselectivity and exo stereoselectivity. The presence of the CF3 group in the β-position in the enol acetate accelerates the 32CA reaction, but it does not modify the regioselectivity, which is controlled by the presence of the ester group. While ortho regioselectivity is reproduced by the MPWB1K calculations, the endo selectivity is not. The inclusion of solvent effects slightly decreases the reactivity but does not modify the gas phase selectivities. Analysis of the DFT global reactivity indices and the Parr functions in reagents provide a rationalization for the participation of ethyl trifluoroacetoacetate and the regioselectivity in this zw-type 32CA reaction. Springer-Verlag Berlin Heidelberg, 2015 [3+2] cycloaddition reaction nationallicence DFT calculations nationallicence DFT reactivity indices nationallicence Enol acetates nationallicence Nitrones nationallicence Regioselectivity nationallicence Solvent effects nationallicence Trifluoromethyl group nationallicence Layeb Hatem Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut Nacereddine Abdelmalek Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut Djerourou Abdelhafid Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut Ríos-Gutiérrez Mar Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain aut Domingo Luis Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain aut Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-9 1610-2940 21:5<1 2015 21 894 https://doi.org/10.1007/s00894-015-2658-5 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 Metadata rights reserved Springer special CC-BY-NC licence nationallicence 1 research-article jats NATIONALLICENCE NATIONALLICENCE NL-springer NATIONALLICENCE 856 40 https://doi.org/10.1007/s00894-015-2658-5 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Layeb Hatem Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut NATIONALLICENCE 700 1- Nacereddine Abdelmalek Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut NATIONALLICENCE 700 1- Djerourou Abdelhafid Synthesis and Biocatalysis Organic Laboratory, Chemistry Department, Faculty of Sciences, Badji Mokhtar University, Annaba, PB 12, 23000, Annaba, Algeria aut NATIONALLICENCE 700 1- Ríos-Gutiérrez Mar Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain aut NATIONALLICENCE 700 1- Domingo Luis Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100, Burjassot, Valencia, Spain aut NATIONALLICENCE 773 0- Journal of Molecular Modeling Springer Berlin Heidelberg 21/5(2015-05-01), 1-9 1610-2940 21:5<1 2015 21 894