Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights
Abstract Efficient synthesis of 3‐arylquinolin‐2(1H)‐ones and N‐(2‐carboxyaryl)‐oxalamides from protic acid‐catalyzed rearrangements of 3‐aryloxirane‐2‐carboxamides was achieved recently but not well understood. In contrast to the classical Meinwald rearrangement, extensive DFT calculations reveal t...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2020-07-01
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| Series: | ChemistryOpen |
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| Online Access: | https://doi.org/10.1002/open.202000110 |
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| author | Dr. Zheng‐Wang Qu Dr. Hui Zhu Prof. Sergey A. Katsyuba Dr. Vera L. Mamedova Prof. Vakhid A. Mamedov Prof. Stefan Grimme |
| author_facet | Dr. Zheng‐Wang Qu Dr. Hui Zhu Prof. Sergey A. Katsyuba Dr. Vera L. Mamedova Prof. Vakhid A. Mamedov Prof. Stefan Grimme |
| author_sort | Dr. Zheng‐Wang Qu |
| collection | DOAJ |
| description | Abstract Efficient synthesis of 3‐arylquinolin‐2(1H)‐ones and N‐(2‐carboxyaryl)‐oxalamides from protic acid‐catalyzed rearrangements of 3‐aryloxirane‐2‐carboxamides was achieved recently but not well understood. In contrast to the classical Meinwald rearrangement, extensive DFT calculations reveal that the proximal aryl and amide groups have strong synergetic effects to control the amide‐aided and aryl‐directed oxirane‐opening and further rearrangement sequences. The ortho‐nitro substituent of the proximal aryl is directly involved in a nucleophilic oxirane ring‐opening, the amide C=O is an important proton shuttle for facile H‐shifts, while the N‐aryl may act as a potential ring‐closing site via Friedel‐Crafts alkylation. The mechanistic insights are useful for rational design of novel synthesis by changing the aryl and amide functional groups proximal to the oxirane ring. |
| first_indexed | 2024-12-17T21:51:01Z |
| format | Article |
| id | doaj.art-0e57579739784020aa3f8b9333b298d8 |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-12-17T21:51:01Z |
| publishDate | 2020-07-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-0e57579739784020aa3f8b9333b298d82022-12-21T21:31:17ZengWiley-VCHChemistryOpen2191-13632020-07-019774374710.1002/open.202000110Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic InsightsDr. Zheng‐Wang Qu0Dr. Hui Zhu1Prof. Sergey A. Katsyuba2Dr. Vera L. Mamedova3Prof. Vakhid A. Mamedov4Prof. Stefan Grimme5Mulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn GermanyMulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn GermanyArbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan RussiaArbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan RussiaArbuzov Institute of Organic and Physical Chemistry FRC Kazan Scientific Center of RAS Arbuzov Str. 8 420088 Kazan RussiaMulliken Center for Theoretical Chemistry University of Bonn Beringstr. 4 53115 Bonn GermanyAbstract Efficient synthesis of 3‐arylquinolin‐2(1H)‐ones and N‐(2‐carboxyaryl)‐oxalamides from protic acid‐catalyzed rearrangements of 3‐aryloxirane‐2‐carboxamides was achieved recently but not well understood. In contrast to the classical Meinwald rearrangement, extensive DFT calculations reveal that the proximal aryl and amide groups have strong synergetic effects to control the amide‐aided and aryl‐directed oxirane‐opening and further rearrangement sequences. The ortho‐nitro substituent of the proximal aryl is directly involved in a nucleophilic oxirane ring‐opening, the amide C=O is an important proton shuttle for facile H‐shifts, while the N‐aryl may act as a potential ring‐closing site via Friedel‐Crafts alkylation. The mechanistic insights are useful for rational design of novel synthesis by changing the aryl and amide functional groups proximal to the oxirane ring.https://doi.org/10.1002/open.202000110DFT calculationssynergetic effectsoxirane openingacid catalysisreaction mechanism |
| spellingShingle | Dr. Zheng‐Wang Qu Dr. Hui Zhu Prof. Sergey A. Katsyuba Dr. Vera L. Mamedova Prof. Vakhid A. Mamedov Prof. Stefan Grimme Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights ChemistryOpen DFT calculations synergetic effects oxirane opening acid catalysis reaction mechanism |
| title | Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights |
| title_full | Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights |
| title_fullStr | Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights |
| title_full_unstemmed | Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights |
| title_short | Acid‐Catalyzed Rearrangements of 3‐Aryloxirane‐2‐Carboxamides: Novel DFT Mechanistic Insights |
| title_sort | acid catalyzed rearrangements of 3 aryloxirane 2 carboxamides novel dft mechanistic insights |
| topic | DFT calculations synergetic effects oxirane opening acid catalysis reaction mechanism |
| url | https://doi.org/10.1002/open.202000110 |
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