This article is published in Journal of Physical Organic Chemistry as a special issue on 13th European Symposium on Organic Reactivity edited by Peeter Burk (University of Tartu, Institute of Chemistry, 2 Jakobi St., Tartu, 51014, Estonia) and Marie-Francoise Ruasse (Université Paris VII-CNRSItODYS, ITODYS, 15 rue Jean de Baïf, 75205 PARIS CEDEX 13, PARIS, 75205, France).
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Research Article
Charge-based DFT descriptors for Diels-Alder reactions†
Article first published online: 4 JUL 2012
DOI: 10.1002/poc.2987
Copyright © 2012 John Wiley & Sons, Ltd.
Issue
Journal of Physical Organic Chemistry
Special Issue: 13th European Symposium on Organic Reactivity
Volume 26, Issue 2, pages 187–193, February 2013
Additional Information
How to Cite
, and (2013), Charge-based DFT descriptors for Diels-Alder reactions. J. Phys. Org. Chem. doi: 10.1002/poc.2987
- †
Publication History
- Issue published online: 25 JAN 2013
- Article first published online: 4 JUL 2012
- Manuscript Accepted: 21 MAY 2012
- Manuscript Revised: 9 APR 2012
- Manuscript Received: 7 SEP 2011
Chemistry Terms
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Keywords:
- Diels-Alder reaction;
- net reactivity index;
- electrophilicity difference;
- fractional number of electron transferred;
- energy lowering;
- electrophilicity-based charge transfer
The geometries of 8 dienes and 18 dienophiles are optimized at the B3LYP/6-311 + G (d) level. The ionization potential (I), electron affinity (A), electronegativity (χ), hardness (η), chemical potential (μ), global electrophilicity (ω), electron accepting power (ω+) and electron donating power (ω−) values are computed employing ΔSCF method. The net reactivity index (Δ
), electrophilicity difference of the reactants (Δω), the fractional number of electrons transferred (ΔN), energy change (ΔE) and electrophilicity-based charge transfer descriptor (ECT) for the Diels-Alder (DA) reactions are computed. Charge-based descriptors like ΔN, ΔE and ECT exhibit good quadratic / linear correlation with 
of the diene to dienophile electron flow (DDpF) type of DA reactions. Δω has also reasonably good quadratic / linear correlation with ΔN, ΔE ECT and
. Charge-based descriptors like ΔN, ΔE and ECT have relatively worse correlation (quadratic / linear) with 
of the dienophile to diene electron flow (DpDF) type of DA reactions. Δω has also similar poor correlation (quadratic / linear) with ΔN, ΔE, ECT and 
for these types of reactions. It can be concluded that charge-based Density Functional Theory (DFT) descriptors can illustrate the DDpF type of DA reactions properly. A possible reason for not so good correlation in the case of DpDF-type reactions is provided. The charges of the reactive sites of the dienes and dienophiles are also computed with the Mulliken population analysis and natural population analysis schemes at the same level of theory. Copyright © 2012 John Wiley & Sons, Ltd.
Featured Compounds
| Compound 23 | |
|---|---|
| Molecular Weight: | 66.1011 |
| Molecular Formula: | C5H6 |
| InChIKey: | ZSWFCLXCOIISFI-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 2 | |
|---|---|
| Molecular Weight: | 128.091 |
| Molecular Formula: | C6N4 |
| InChIKey: | NLDYACGHTUPAQU-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 4 | |
|---|---|
| Molecular Weight: | 98.0569 |
| Molecular Formula: | C4H2O3 |
| InChIKey: | Not Available |
| View compound in article | Full details | Search this compound | |
| Compound 6 | |
|---|---|
| Molecular Weight: | 78.0721 |
| Molecular Formula: | C4H2N2 |
| InChIKey: | FCYVWWWTHPPJII-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 7 | |
|---|---|
| Molecular Weight: | 73.0507 |
| Molecular Formula: | C2H3NO2 |
| InChIKey: | RPMXALUWKZHYOV-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 10 | |
|---|---|
| Molecular Weight: | 144.1253 |
| Molecular Formula: | C6H8O4 |
| InChIKey: | KTLZQSZGORXBED-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 11 | |
|---|---|
| Molecular Weight: | 142.1094 |
| Molecular Formula: | C6H6O4 |
| InChIKey: | VHILMKFSCRWWIJ-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 13 | |
|---|---|
| Molecular Weight: | 84.0734 |
| Molecular Formula: | C4H4O2 |
| InChIKey: | IMAKHNTVDGLIRY-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 21 | |
|---|---|
| Molecular Weight: | 82.1436 |
| Molecular Formula: | C6H10 |
| InChIKey: | CJSBUWDGPXGFGA-UHFFFAOYSA-N |
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| Compound 24 | |
|---|---|
| Molecular Weight: | 84.1164 |
| Molecular Formula: | C5H8O |
| InChIKey: | KOCUMXQOUWPSLK-SNAWJCMRSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 25 | |
|---|---|
| Molecular Weight: | 142.271 |
| Molecular Formula: | C7H14OSi |
| InChIKey: | Not Available |
| View compound in article | Full details | Search this compound | |
| Compound 28 | |
|---|---|
| Molecular Weight: | 97.1582 |
| Molecular Formula: | C6H11N |
| InChIKey: | VNIQZQGVXVYHSP-AATRIKPKSA-N |
| View compound in article | Full details | Search this compound | |
| Compound 30 | |
|---|---|
| Molecular Weight: | 67.0892 |
| Molecular Formula: | C4H5N |
| InChIKey: | KAESVJOAVNADME-UHFFFAOYSA-N |
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| Compound 31 | |
|---|---|
| Molecular Weight: | 82.1005 |
| Molecular Formula: | C5H6O |
| InChIKey: | VQKFNUFAXTZWDK-UHFFFAOYSA-N |
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| Compound 32 | |
|---|---|
| Molecular Weight: | 71.121 |
| Molecular Formula: | C4H9N |
| InChIKey: | NINOYJQVULROET-UHFFFAOYSA-N |
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| Compound 1 | |
|---|---|
| Molecular Weight: | 170.9802 |
| Molecular Formula: | C2H6IN |
| InChIKey: | RHMCYHBFTRZERD-UHFFFAOYSA-N |
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| Compound 3 | |
|---|---|
| Molecular Weight: | 182.088 |
| Molecular Formula: | C3F6S |
| InChIKey: | DBNMHLDZMPEZCX-UHFFFAOYSA-N |
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| Compound 5 | |
|---|---|
| Molecular Weight: | 69.898 |
| Molecular Formula: | C3H7BO |
| InChIKey: | HHMLJEYWAPWHOK-UHFFFAOYSA-N |
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| Compound 12 | |
|---|---|
| Molecular Weight: | 70.0898 |
| Molecular Formula: | C4H6O |
| InChIKey: | FUSUHKVFWTUUBE-UHFFFAOYSA-N |
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| Compound 14 | |
|---|---|
| Molecular Weight: | 86.0892 |
| Molecular Formula: | C4H6O2 |
| InChIKey: | BAPJBEWLBFYGME-UHFFFAOYSA-N |
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| Compound 27 | |
|---|---|
| Molecular Weight: | 68.074 |
| Molecular Formula: | C4H4O |
| InChIKey: | YLQBMQCUIZJEEH-UHFFFAOYSA-N |
| View compound in article | Full details | Search this compound | |