caa a22 4500 605488142 CHVBK 20210128100454.0 cr unu---uuuuu 210128e20150801xx s 000 0 eng 10.1007/s00214-015-1694-7 doi (NATIONALLICENCE)springer-10.1007/s00214-015-1694-7 Allylation of active methylene compounds with cyclic Baylis-Hillman alcohols: a DFT study [Elektronische Daten] [Karim Harrath, Khaled Essalah, Christophe Morell, Henry Chermette, Salima Boughdiri] Allylation reaction of active methylene compounds with cyclic Baylis-Hillman (BH) alcohol catalyzed by 4-dimethyamino-pyridine (DMAP) has been investigated by means of density functional theory with B3LYP/6-311++G(d,p). The first step on the chemical path is considered as an acid-base reaction. It is then followed by allylation of active methylene compound with cyclic BH alcohol. Calculated gas-phase pKa values illustrate that active methylene compounds have higher acidity than the considered cyclic BH alcohol. The DMAP catalytic activity may be interpreted as a proton transfer bridge between the active methylene compounds and the cyclic BH alcohol. Two alternative competing reactivity sites are present. Regioselectivity has been carried out on the base of natural atomic charge, Fukui index. The computations help rationalizing the fact that the direct allylation is the favored reaction and leads to the end-product. Springer-Verlag Berlin Heidelberg, 2015 DFT calculation nationallicence Gas-phase pKa nationallicence Theoretical mechanism nationallicence Klopman-Salem nationallicence Orbital control nationallicence Charge control nationallicence Fukui function nationallicence Transition state nationallicence Harrath Karim Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia aut Essalah Khaled Research Unity of Molecular Physico-Chemistry, IPEST, Marsa, BP 51, 2070, Tunis, Tunisia aut Morell Christophe University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France aut Chermette Henry University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France aut Boughdiri Salima Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia aut Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-12 1432-881X 134:8<1 2015 134 214 https://doi.org/10.1007/s00214-015-1694-7 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/s00214-015-1694-7 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Harrath Karim Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia aut NATIONALLICENCE 700 1- Essalah Khaled Research Unity of Molecular Physico-Chemistry, IPEST, Marsa, BP 51, 2070, Tunis, Tunisia aut NATIONALLICENCE 700 1- Morell Christophe University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France aut NATIONALLICENCE 700 1- Chermette Henry University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France aut NATIONALLICENCE 700 1- Boughdiri Salima Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia aut NATIONALLICENCE 773 0- Theoretical Chemistry Accounts Springer Berlin Heidelberg 134/8(2015-08-01), 1-12 1432-881X 134:8<1 2015 134 214