A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives
The present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA) and an intramolecular 1,3-dipolar cycloaddition (IMDCA) of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysi...
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Serbian Chemical Society
2014-01-01
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| Series: | Journal of the Serbian Chemical Society |
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| Online Access: | http://www.doiserbia.nb.rs/img/doi/0352-5139/2014/0352-51391400012H.pdf |
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doaj-18cd524bd7dd442d887de6da48a2190e2020-11-24T23:13:08ZengSerbian Chemical Society Journal of the Serbian Chemical Society0352-51391820-74212014-01-0179891192410.2298/JSC140121012H0352-51391400012HA theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivativesHamzehloueian Mahshid0Yeganegi Saeid1Sarrafi Yaghoub2Alimohammadi Kamal3Sadatshahabi Marzieh4Department of Chemistry, Islamic Azad University, Jouybar Branch, Jouybar, IranDepartment of Physical Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, IranDepartment of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, IranDepartment of Chemistry, Dr. Ali Shariati branch, University of Farhangian, Sari, IranDepartment of Organic Chemistry, Faculty of Chemistry, University of Mazandaran, Babolsar, IranThe present study reports a systematic computational analysis of the two possible pathways, fused and bridged, for an intramolecular hetero Diels-Alder (IMHDA) and an intramolecular 1,3-dipolar cycloaddition (IMDCA) of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis for both reactions is in agreement with experimental observations. The activation energies associated with the two regioisomeric channels in IMHDA reaction show that the bridged product is favored, although in IMDCA, the most stable TS results the fused product. The global electronic properties of fragments within each molecule were studied to discuss the reactivity patterns and charge transfer direction in the intramolecular processes. The asynchronicity of the bond formation and aromaticity of the optimized TSs in the Diels-Alder reaction as well as cycloaddition reaction were evaluated. Finally, 1H NMR chemical shifts of the possible regioisomers have been calculated using the GIAO method which of the most stable products are in agreement with the experimental data in the both reaction.http://www.doiserbia.nb.rs/img/doi/0352-5139/2014/0352-51391400012H.pdfintramolecular hetero Diels-Alderintramolecular 1,3-dipolar cycloadditioncharge transferDFT calculationfragment electrophicity analysis |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Hamzehloueian Mahshid Yeganegi Saeid Sarrafi Yaghoub Alimohammadi Kamal Sadatshahabi Marzieh |
| spellingShingle |
Hamzehloueian Mahshid Yeganegi Saeid Sarrafi Yaghoub Alimohammadi Kamal Sadatshahabi Marzieh A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives Journal of the Serbian Chemical Society intramolecular hetero Diels-Alder intramolecular 1,3-dipolar cycloaddition charge transfer DFT calculation fragment electrophicity analysis |
| author_facet |
Hamzehloueian Mahshid Yeganegi Saeid Sarrafi Yaghoub Alimohammadi Kamal Sadatshahabi Marzieh |
| author_sort |
Hamzehloueian Mahshid |
| title |
A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| title_short |
A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| title_full |
A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| title_fullStr |
A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| title_full_unstemmed |
A theoretical investigation on the regioselectivity of the intramolecular hetero Diels-Alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| title_sort |
theoretical investigation on the regioselectivity of the intramolecular hetero diels-alder and 1,3-dipolar cycloaddition of 2-vinyloxybenzaldehyde derivatives |
| publisher |
Serbian Chemical Society |
| series |
Journal of the Serbian Chemical Society |
| issn |
0352-5139 1820-7421 |
| publishDate |
2014-01-01 |
| description |
The present study reports a systematic computational analysis of the two
possible pathways, fused and bridged, for an intramolecular hetero
Diels-Alder (IMHDA) and an intramolecular 1,3-dipolar cycloaddition (IMDCA)
of 2-vinyloxybenzaldehyde derivatives. The potential energy surface analysis
for both reactions is in agreement with experimental observations. The
activation energies associated with the two regioisomeric channels in IMHDA
reaction show that the bridged product is favored, although in IMDCA, the
most stable TS results the fused product. The global electronic properties
of fragments within each molecule were studied to discuss the reactivity
patterns and charge transfer direction in the intramolecular processes. The
asynchronicity of the bond formation and aromaticity of the optimized TSs in
the Diels-Alder reaction as well as cycloaddition reaction were evaluated.
Finally, 1H NMR chemical shifts of the possible regioisomers have been
calculated using the GIAO method which of the most stable products are in
agreement with the experimental data in the both reaction. |
| topic |
intramolecular hetero Diels-Alder intramolecular 1,3-dipolar cycloaddition charge transfer DFT calculation fragment electrophicity analysis |
| url |
http://www.doiserbia.nb.rs/img/doi/0352-5139/2014/0352-51391400012H.pdf |
| work_keys_str_mv |
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| _version_ |
1725599156166197248 |