Triethylamine-Promoted Oxidative Cyclodimerization of 2H-Azirine-2-carboxylates to Pyrimidine-4,6-dicarboxylates : Experimental and DFT Study
An unprecedented oxidative cyclodimerization reaction of 2H-azirine-2-carboxylates to pyrimidine-4,6-dicarboxylates under heating with triethylamine in air is described. In this reaction, one azirine molecule undergoes formal cleavage across the C-C bond and another across the C=N bond. According to the experimental study and DFT calculations, the key steps of the reaction mechanism include nucleophilic addition of N,N-diethylhydroxylamine to an azirine to form an (aminooxy)aziridine, generation of an azomethine ylide, and its 1,3-dipolar cycloaddition to the second azirine molecule. The crucial condition for the synthesis of pyrimidines is generation of N,N-diethylhydroxylamine in the reaction mixture in a very low concentration, which is ensured by the slow oxidation of triethylamine with air oxygen. Addition of a radical initiator accelerated the reaction and resulted in higher yields of the pyrimidines. Under these conditions, the scope of the pyrimidine formation was elucidated, and a series of pyrimidines was synthesized.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:28 |
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| Enthalten in: |
Molecules (Basel, Switzerland) - 28(2023), 11 vom: 24. Mai |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Zakharov, Timofei N [VerfasserIn] |
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| Links: |
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| Anmerkungen: |
Date Completed 12.06.2023 Date Revised 12.06.2023 published: Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.3390/molecules28114315 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM358005442 |
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| 100 | 1 | |a Zakharov, Timofei N |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Triethylamine-Promoted Oxidative Cyclodimerization of 2H-Azirine-2-carboxylates to Pyrimidine-4,6-dicarboxylates |b Experimental and DFT Study |
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| 500 | |a Date Completed 12.06.2023 | ||
| 500 | |a Date Revised 12.06.2023 | ||
| 500 | |a published: Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a An unprecedented oxidative cyclodimerization reaction of 2H-azirine-2-carboxylates to pyrimidine-4,6-dicarboxylates under heating with triethylamine in air is described. In this reaction, one azirine molecule undergoes formal cleavage across the C-C bond and another across the C=N bond. According to the experimental study and DFT calculations, the key steps of the reaction mechanism include nucleophilic addition of N,N-diethylhydroxylamine to an azirine to form an (aminooxy)aziridine, generation of an azomethine ylide, and its 1,3-dipolar cycloaddition to the second azirine molecule. The crucial condition for the synthesis of pyrimidines is generation of N,N-diethylhydroxylamine in the reaction mixture in a very low concentration, which is ensured by the slow oxidation of triethylamine with air oxygen. Addition of a radical initiator accelerated the reaction and resulted in higher yields of the pyrimidines. Under these conditions, the scope of the pyrimidine formation was elucidated, and a series of pyrimidines was synthesized | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a DFT calculations | |
| 650 | 4 | |a aziridines | |
| 650 | 4 | |a azirines | |
| 650 | 4 | |a azomethine ylides | |
| 650 | 4 | |a cycloaddition | |
| 650 | 4 | |a cyclodimerization | |
| 650 | 4 | |a hippurates | |
| 650 | 4 | |a hydroxylamines | |
| 650 | 4 | |a pyrimidines | |
| 650 | 4 | |a triethylamine | |
| 650 | 7 | |a pyrimidine-4,6-dicarboxylate |2 NLM | |
| 650 | 7 | |a N,N-diethylhydroxylamine |2 NLM | |
| 650 | 7 | |a 314I05EDVH |2 NLM | |
| 650 | 7 | |a triethylamine |2 NLM | |
| 650 | 7 | |a VOU728O6AY |2 NLM | |
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| 650 | 7 | |a pyrimidine |2 NLM | |
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| 650 | 7 | |a Pyrimidines |2 NLM | |
| 700 | 1 | |a Sakharov, Pavel A |e verfasserin |4 aut | |
| 700 | 1 | |a Novikov, Mikhail S |e verfasserin |4 aut | |
| 700 | 1 | |a Khlebnikov, Alexander F |e verfasserin |4 aut | |
| 700 | 1 | |a Rostovskii, Nikolai V |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.3390/molecules28114315 |3 Volltext |
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