Mechanistic investigations on Pinnick oxidation: a density functional theory study
A computational study on Pinnick oxidation of aldehydes into carboxylic acids using density functional theory (DFT) calculations has been evaluated with the (SMD)-M06-2X/aug-pVDZ level of theory, leading to an important understanding of the reaction mechanism that agrees with the experimental observ...
| Main Authors: | , , , , , , , |
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| Format: | Article |
| Language: | English |
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The Royal Society
2020-02-01
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| Series: | Royal Society Open Science |
| Subjects: | |
| Online Access: | https://royalsocietypublishing.org/doi/pdf/10.1098/rsos.191568 |
| _version_ | 1818392109562986496 |
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| author | Aqeel A. Hussein Azzam A. M. Al-Hadedi Alaa J. Mahrath Gamal A. I. Moustafa Faisal A. Almalki Alaa Alqahtani Sergey Shityakov Moaed E. Algazally |
| author_facet | Aqeel A. Hussein Azzam A. M. Al-Hadedi Alaa J. Mahrath Gamal A. I. Moustafa Faisal A. Almalki Alaa Alqahtani Sergey Shityakov Moaed E. Algazally |
| author_sort | Aqeel A. Hussein |
| collection | DOAJ |
| description | A computational study on Pinnick oxidation of aldehydes into carboxylic acids using density functional theory (DFT) calculations has been evaluated with the (SMD)-M06-2X/aug-pVDZ level of theory, leading to an important understanding of the reaction mechanism that agrees with the experimental observations and explaining the substantial role of acid in driving the reaction. The DFT results elucidated that the first reaction step (FRS) proceeds in a manner where chlorous acid reacts with the aldehyde group through a distorted six-membered ring transition state to give a hydroxyallyl chlorite intermediate that undergoes a pericyclic fragmentation to release the carboxylic acid as a second reaction step (SRS). 1H NMR experiments and simulations showed that hydrogen bonding between carbonyl and t-butanol is unlikely to occur. Additionally, it was found that the FRS is a rate-determining and thermoneutral step, whereas SRS is highly exergonic with a low energetic barrier due to the Cl(III) → Cl(II) reduction. Frontier molecular orbital analysis, intrinsic reaction coordinate, molecular dynamics and distortion/interaction analysis further supported the proposed mechanism. |
| first_indexed | 2024-12-14T05:24:12Z |
| format | Article |
| id | doaj.art-4813370494b14ade823cbb8a3344b2fd |
| institution | Directory Open Access Journal |
| issn | 2054-5703 |
| language | English |
| last_indexed | 2024-12-14T05:24:12Z |
| publishDate | 2020-02-01 |
| publisher | The Royal Society |
| record_format | Article |
| series | Royal Society Open Science |
| spelling | doaj.art-4813370494b14ade823cbb8a3344b2fd2022-12-21T23:15:34ZengThe Royal SocietyRoyal Society Open Science2054-57032020-02-017210.1098/rsos.191568191568Mechanistic investigations on Pinnick oxidation: a density functional theory studyAqeel A. HusseinAzzam A. M. Al-HadediAlaa J. MahrathGamal A. I. MoustafaFaisal A. AlmalkiAlaa AlqahtaniSergey ShityakovMoaed E. AlgazallyA computational study on Pinnick oxidation of aldehydes into carboxylic acids using density functional theory (DFT) calculations has been evaluated with the (SMD)-M06-2X/aug-pVDZ level of theory, leading to an important understanding of the reaction mechanism that agrees with the experimental observations and explaining the substantial role of acid in driving the reaction. The DFT results elucidated that the first reaction step (FRS) proceeds in a manner where chlorous acid reacts with the aldehyde group through a distorted six-membered ring transition state to give a hydroxyallyl chlorite intermediate that undergoes a pericyclic fragmentation to release the carboxylic acid as a second reaction step (SRS). 1H NMR experiments and simulations showed that hydrogen bonding between carbonyl and t-butanol is unlikely to occur. Additionally, it was found that the FRS is a rate-determining and thermoneutral step, whereas SRS is highly exergonic with a low energetic barrier due to the Cl(III) → Cl(II) reduction. Frontier molecular orbital analysis, intrinsic reaction coordinate, molecular dynamics and distortion/interaction analysis further supported the proposed mechanism.https://royalsocietypublishing.org/doi/pdf/10.1098/rsos.191568pinnick oxidationdensity functional theory simulationstransition statemolecular dynamicsmolecular orbital theoryoxidation |
| spellingShingle | Aqeel A. Hussein Azzam A. M. Al-Hadedi Alaa J. Mahrath Gamal A. I. Moustafa Faisal A. Almalki Alaa Alqahtani Sergey Shityakov Moaed E. Algazally Mechanistic investigations on Pinnick oxidation: a density functional theory study Royal Society Open Science pinnick oxidation density functional theory simulations transition state molecular dynamics molecular orbital theory oxidation |
| title | Mechanistic investigations on Pinnick oxidation: a density functional theory study |
| title_full | Mechanistic investigations on Pinnick oxidation: a density functional theory study |
| title_fullStr | Mechanistic investigations on Pinnick oxidation: a density functional theory study |
| title_full_unstemmed | Mechanistic investigations on Pinnick oxidation: a density functional theory study |
| title_short | Mechanistic investigations on Pinnick oxidation: a density functional theory study |
| title_sort | mechanistic investigations on pinnick oxidation a density functional theory study |
| topic | pinnick oxidation density functional theory simulations transition state molecular dynamics molecular orbital theory oxidation |
| url | https://royalsocietypublishing.org/doi/pdf/10.1098/rsos.191568 |
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