The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones
Diarylheptanoids have been reported as biosynthetic precursors of phenylphenalenones in plants. Quantum chemical calculations of molecular geometry and orbitals were used to elaborate which structural features are required to determine if diarylheptanoids can undergo an intramolecular Diel-Alder r...
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MDPI AG
2014-04-01
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| Series: | Molecules |
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| Online Access: | http://www.mdpi.com/1420-3049/19/4/5231 |
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| author | Yulia Monakhova Bernd Schneider |
| author_facet | Yulia Monakhova Bernd Schneider |
| author_sort | Yulia Monakhova |
| collection | DOAJ |
| description | Diarylheptanoids have been reported as biosynthetic precursors of phenylphenalenones in plants. Quantum chemical calculations of molecular geometry and orbitals were used to elaborate which structural features are required to determine if diarylheptanoids can undergo an intramolecular Diel-Alder reaction to form phenylphenalenones. The computational data showed that an ortho-quinone- or a hydoxyketone-bearing ring A, containing the dienophile moiety, and a heptadiene chain with conjugated cisoid double bonds at C-4/C-6 and a saturated segment consisting of two sp3-carbon atoms, are required. Only four diarylheptanoids out of eighteen studied compounds proved to be suitable candidates. Among them are two 3,5-dideoxy compounds and two other compounds oxygenated only at C-3, suggesting that lachnanthocarpone, a representative of the 6-oxygenated phenylphenalenones, and anigorufone, a representative of the 6-deoxy phenylphenalenones, are not connected via a precursor-product relationship (“late reduction at C-6”) but formed through partially separate pathways. |
| first_indexed | 2024-12-11T08:34:04Z |
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| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-11T08:34:04Z |
| publishDate | 2014-04-01 |
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| series | Molecules |
| spelling | doaj.art-ab881f99f9de4206a9e59ede114d3a3a2022-12-22T01:14:24ZengMDPI AGMolecules1420-30492014-04-011945231524210.3390/molecules19045231molecules19045231The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of PhenylphenalenonesYulia Monakhova0Bernd Schneider1Department of Chemistry, Saratov State University, Astrakhanskaya Street 83, Saratov 410012, RussiaMax Planck Institute for Chemical Ecology, Hans Knöll-Str. 8, Jena 07745, GermanyDiarylheptanoids have been reported as biosynthetic precursors of phenylphenalenones in plants. Quantum chemical calculations of molecular geometry and orbitals were used to elaborate which structural features are required to determine if diarylheptanoids can undergo an intramolecular Diel-Alder reaction to form phenylphenalenones. The computational data showed that an ortho-quinone- or a hydoxyketone-bearing ring A, containing the dienophile moiety, and a heptadiene chain with conjugated cisoid double bonds at C-4/C-6 and a saturated segment consisting of two sp3-carbon atoms, are required. Only four diarylheptanoids out of eighteen studied compounds proved to be suitable candidates. Among them are two 3,5-dideoxy compounds and two other compounds oxygenated only at C-3, suggesting that lachnanthocarpone, a representative of the 6-oxygenated phenylphenalenones, and anigorufone, a representative of the 6-deoxy phenylphenalenones, are not connected via a precursor-product relationship (“late reduction at C-6”) but formed through partially separate pathways.http://www.mdpi.com/1420-3049/19/4/5231diarylheptanoids(4+2)-cycloadditionDiels-Alder reactionphenylphenalenonesquantum chemistry6-31G*molecular orbitals |
| spellingShingle | Yulia Monakhova Bernd Schneider The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones Molecules diarylheptanoids (4+2)-cycloaddition Diels-Alder reaction phenylphenalenones quantum chemistry 6-31G* molecular orbitals |
| title | The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones |
| title_full | The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones |
| title_fullStr | The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones |
| title_full_unstemmed | The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones |
| title_short | The Intramolecular Diels-Alder Reaction of Diarylheptanoids — Quantum Chemical Calculation of Structural Features Favoring the Formation of Phenylphenalenones |
| title_sort | intramolecular diels alder reaction of diarylheptanoids quantum chemical calculation of structural features favoring the formation of phenylphenalenones |
| topic | diarylheptanoids (4+2)-cycloaddition Diels-Alder reaction phenylphenalenones quantum chemistry 6-31G* molecular orbitals |
| url | http://www.mdpi.com/1420-3049/19/4/5231 |
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