Allylation of active methylene compounds with cyclic Baylis-Hillman alcohols: a DFT study
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| 024 | 7 | 0 | |a 10.1007/s00214-015-1694-7 |2 doi |
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| 245 | 0 | 0 | |a Allylation of active methylene compounds with cyclic Baylis-Hillman alcohols: a DFT study |h [Elektronische Daten] |c [Karim Harrath, Khaled Essalah, Christophe Morell, Henry Chermette, Salima Boughdiri] |
| 520 | 3 | |a 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. | |
| 540 | |a Springer-Verlag Berlin Heidelberg, 2015 | ||
| 690 | 7 | |a DFT calculation |2 nationallicence | |
| 690 | 7 | |a Gas-phase pKa |2 nationallicence | |
| 690 | 7 | |a Theoretical mechanism |2 nationallicence | |
| 690 | 7 | |a Klopman-Salem |2 nationallicence | |
| 690 | 7 | |a Orbital control |2 nationallicence | |
| 690 | 7 | |a Charge control |2 nationallicence | |
| 690 | 7 | |a Fukui function |2 nationallicence | |
| 690 | 7 | |a Transition state |2 nationallicence | |
| 700 | 1 | |a Harrath |D Karim |u Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia |4 aut | |
| 700 | 1 | |a Essalah |D Khaled |u Research Unity of Molecular Physico-Chemistry, IPEST, Marsa, BP 51, 2070, Tunis, Tunisia |4 aut | |
| 700 | 1 | |a Morell |D Christophe |u University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France |4 aut | |
| 700 | 1 | |a Chermette |D Henry |u University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France |4 aut | |
| 700 | 1 | |a Boughdiri |D Salima |u Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia |4 aut | |
| 773 | 0 | |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/8(2015-08-01), 1-12 |x 1432-881X |q 134:8<1 |1 2015 |2 134 |o 214 | |
| 856 | 4 | 0 | |u https://doi.org/10.1007/s00214-015-1694-7 |q text/html |z Onlinezugriff via DOI |
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 900 | 7 | |a Metadata rights reserved |b Springer special CC-BY-NC licence |2 nationallicence | |
| 908 | |D 1 |a research-article |2 jats | ||
| 949 | |B NATIONALLICENCE |F NATIONALLICENCE |b NL-springer | ||
| 950 | |B NATIONALLICENCE |P 856 |E 40 |u https://doi.org/10.1007/s00214-015-1694-7 |q text/html |z Onlinezugriff via DOI | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Harrath |D Karim |u Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Essalah |D Khaled |u Research Unity of Molecular Physico-Chemistry, IPEST, Marsa, BP 51, 2070, Tunis, Tunisia |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Morell |D Christophe |u University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Chermette |D Henry |u University Lyon 1(UCBL) and CNRS UMR 5280 Institut Sciences Analytiques, Université de Lyon, 69622, Villeurbanne Cedex, France |4 aut | ||
| 950 | |B NATIONALLICENCE |P 700 |E 1- |a Boughdiri |D Salima |u Research Unity of Physical Chemistry Condensed Materials, Department of Chemistry, Faculty of Sciences, University Tunis El Manar, 2092, Tunis, Tunisia |4 aut | ||
| 950 | |B NATIONALLICENCE |P 773 |E 0- |t Theoretical Chemistry Accounts |d Springer Berlin Heidelberg |g 134/8(2015-08-01), 1-12 |x 1432-881X |q 134:8<1 |1 2015 |2 134 |o 214 | ||