1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents
An effective synthesis of the hitherto unknown 1-imidoalkylphosphonium salts has been developed in the reported study. The crucial step in the method included the decarboxylative α-methoxylation of N-phthaloyl- or N-succinylamino acids to the corresponding N-(1-methoxyalkyl)imides, followed by the d...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2017-07-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.13.142 |
| _version_ | 1818578558802460672 |
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| author | Jakub Adamek Roman Mazurkiewicz Anna Węgrzyk Karol Erfurt |
| author_facet | Jakub Adamek Roman Mazurkiewicz Anna Węgrzyk Karol Erfurt |
| author_sort | Jakub Adamek |
| collection | DOAJ |
| description | An effective synthesis of the hitherto unknown 1-imidoalkylphosphonium salts has been developed in the reported study. The crucial step in the method included the decarboxylative α-methoxylation of N-phthaloyl- or N-succinylamino acids to the corresponding N-(1-methoxyalkyl)imides, followed by the displacement of the methoxy group by the triarylphosphonium group through melting of the imide derivative with triarylphosphonium tetrafluoroborate. The imidoalkylating properties of the obtained 1-imidoalkylphosphonium salts were tested using the Tscherniac–Einhorn-type reaction with aromatic hydrocarbons as a model reaction. It was found that the Cα–P+ bond strength can be considerably reduced and the imidoalkylation of arenes can be markedly facilitated using 1-imidoalkylphosphonium salts derived from triarylphosphines with electron-withdrawing substituents such as tris(m-chorophenyl)phosphine, tris(p-chlorophenyl)phosphine and tris[p-(trifluoromethyl)phenyl]phosphine. Microwave irradiation also considerably facilitates the cleavage of the highly polar Cα–P+ bond. |
| first_indexed | 2024-12-16T06:47:43Z |
| format | Article |
| id | doaj.art-9cd57c4aedea4b9c8c08cdeff7c44577 |
| institution | Directory Open Access Journal |
| issn | 1860-5397 |
| language | English |
| last_indexed | 2024-12-16T06:47:43Z |
| publishDate | 2017-07-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj.art-9cd57c4aedea4b9c8c08cdeff7c445772022-12-21T22:40:29ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972017-07-011311446145510.3762/bjoc.13.1421860-5397-13-1421-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agentsJakub Adamek0Roman Mazurkiewicz1Anna Węgrzyk2Karol Erfurt3Department of Organic Chemistry, Bioorganic Chemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Bioorganic Chemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Organic Chemistry, Bioorganic Chemistry and Biotechnology, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandDepartment of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, B. Krzywoustego 4, 44-100 Gliwice, PolandAn effective synthesis of the hitherto unknown 1-imidoalkylphosphonium salts has been developed in the reported study. The crucial step in the method included the decarboxylative α-methoxylation of N-phthaloyl- or N-succinylamino acids to the corresponding N-(1-methoxyalkyl)imides, followed by the displacement of the methoxy group by the triarylphosphonium group through melting of the imide derivative with triarylphosphonium tetrafluoroborate. The imidoalkylating properties of the obtained 1-imidoalkylphosphonium salts were tested using the Tscherniac–Einhorn-type reaction with aromatic hydrocarbons as a model reaction. It was found that the Cα–P+ bond strength can be considerably reduced and the imidoalkylation of arenes can be markedly facilitated using 1-imidoalkylphosphonium salts derived from triarylphosphines with electron-withdrawing substituents such as tris(m-chorophenyl)phosphine, tris(p-chlorophenyl)phosphine and tris[p-(trifluoromethyl)phenyl]phosphine. Microwave irradiation also considerably facilitates the cleavage of the highly polar Cα–P+ bond.https://doi.org/10.3762/bjoc.13.142N-(1-arylalkyl)imidesα-imidoalkylating agentsimidoalkylation reactions1-imidoalkylphosphonium saltsTscherniac–Einhorn-type reaction |
| spellingShingle | Jakub Adamek Roman Mazurkiewicz Anna Węgrzyk Karol Erfurt 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents Beilstein Journal of Organic Chemistry N-(1-arylalkyl)imides α-imidoalkylating agents imidoalkylation reactions 1-imidoalkylphosphonium salts Tscherniac–Einhorn-type reaction |
| title | 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents |
| title_full | 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents |
| title_fullStr | 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents |
| title_full_unstemmed | 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents |
| title_short | 1-Imidoalkylphosphonium salts with modulated Cα–P+ bond strength: synthesis and application as new active α-imidoalkylating agents |
| title_sort | 1 imidoalkylphosphonium salts with modulated cα p bond strength synthesis and application as new active α imidoalkylating agents |
| topic | N-(1-arylalkyl)imides α-imidoalkylating agents imidoalkylation reactions 1-imidoalkylphosphonium salts Tscherniac–Einhorn-type reaction |
| url | https://doi.org/10.3762/bjoc.13.142 |
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