Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands
The synthesis of a palladium complex bearing two diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-nitrophenyl)methyl]phosphonates as ligands has demonstrated the ability of this type of $\alpha $-aminophosphonates to coordinate to the palladium(II) ion via their electronically enriched nitrogen atom o...
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Académie des sciences
2022-02-01
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| Series: | Comptes Rendus. Chimie |
| Subjects: | |
| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.144/ |
| _version_ | 1797517817574064128 |
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| author | Hkiri, Shaima Touil, Soufiane Samarat, Ali Sémeril, David |
| author_facet | Hkiri, Shaima Touil, Soufiane Samarat, Ali Sémeril, David |
| author_sort | Hkiri, Shaima |
| collection | DOAJ |
| description | The synthesis of a palladium complex bearing two diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-nitrophenyl)methyl]phosphonates as ligands has demonstrated the ability of this type of $\alpha $-aminophosphonates to coordinate to the palladium(II) ion via their electronically enriched nitrogen atom of the 1,3,4-oxadiazole ring. The complex was fully characterized by elemental analysis, infrared, NMR and mass spectrometry. A solid-state structure revealed the trans coordination of the two nitrogenated ligands. The presence of a hemilabile P(O)(OEt)$_{2}$ moiety in the $\alpha $-aminophosphonates was exploited into palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl halides. The formation of ($N{,}O$)-chelate intermediates may increase the steric hindrance and the electronic density of the metal, which should favor the oxidative addition and the reductive elimination/product decoordination elementary steps. With our catalytic systems, good activities for the formation of ortho-di/trisubstituted biphenyl compounds were observed from aryl bromides using only 0.5 mol% of palladium. Cross-coupling of aryl chlorides required a catalyst loading of 1 mol% to generate ortho-substituted biphenyls. |
| first_indexed | 2024-03-10T07:21:30Z |
| format | Article |
| id | doaj.art-a6c509fa9d3a402098d2cd0c2e5f708c |
| institution | Directory Open Access Journal |
| issn | 1878-1543 |
| language | English |
| last_indexed | 2024-03-10T07:21:30Z |
| publishDate | 2022-02-01 |
| publisher | Académie des sciences |
| record_format | Article |
| series | Comptes Rendus. Chimie |
| spelling | doaj.art-a6c509fa9d3a402098d2cd0c2e5f708c2023-11-22T14:33:32ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432022-02-0125G1536510.5802/crchim.14410.5802/crchim.144Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligandsHkiri, Shaima0Touil, Soufiane1https://orcid.org/0000-0002-2878-5757Samarat, Ali2https://orcid.org/0000-0002-8334-7565Sémeril, David3https://orcid.org/0000-0002-2582-4191University of Strasbourg, Synthèse Organométallique et Catalyse, UMR-CNRS 7177, 4 rue Blaise Pascal, 67008 Strasbourg, France; University of Carthage, Faculty of Sciences of Bizerte, LR18ES11, Laboratory of Hetero-Organic Compounds and Nanostructured Materials, 7021, Bizerte, TunisiaUniversity of Carthage, Faculty of Sciences of Bizerte, LR18ES11, Laboratory of Hetero-Organic Compounds and Nanostructured Materials, 7021, Bizerte, TunisiaUniversity of Carthage, Faculty of Sciences of Bizerte, LR18ES11, Laboratory of Hetero-Organic Compounds and Nanostructured Materials, 7021, Bizerte, TunisiaUniversity of Strasbourg, Synthèse Organométallique et Catalyse, UMR-CNRS 7177, 4 rue Blaise Pascal, 67008 Strasbourg, FranceThe synthesis of a palladium complex bearing two diethyl[(5-phenyl-1,3,4-oxadiazol-2-ylamino)(4-nitrophenyl)methyl]phosphonates as ligands has demonstrated the ability of this type of $\alpha $-aminophosphonates to coordinate to the palladium(II) ion via their electronically enriched nitrogen atom of the 1,3,4-oxadiazole ring. The complex was fully characterized by elemental analysis, infrared, NMR and mass spectrometry. A solid-state structure revealed the trans coordination of the two nitrogenated ligands. The presence of a hemilabile P(O)(OEt)$_{2}$ moiety in the $\alpha $-aminophosphonates was exploited into palladium-catalyzed Suzuki–Miyaura cross-coupling of aryl halides. The formation of ($N{,}O$)-chelate intermediates may increase the steric hindrance and the electronic density of the metal, which should favor the oxidative addition and the reductive elimination/product decoordination elementary steps. With our catalytic systems, good activities for the formation of ortho-di/trisubstituted biphenyl compounds were observed from aryl bromides using only 0.5 mol% of palladium. Cross-coupling of aryl chlorides required a catalyst loading of 1 mol% to generate ortho-substituted biphenyls.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.144/$\alpha $-Aminophosphonate1,3,4-OxadiazolePalladium catalysisSuzuki–Miyaura cross-couplingHemilabile ligand |
| spellingShingle | Hkiri, Shaima Touil, Soufiane Samarat, Ali Sémeril, David Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands Comptes Rendus. Chimie $\alpha $-Aminophosphonate 1,3,4-Oxadiazole Palladium catalysis Suzuki–Miyaura cross-coupling Hemilabile ligand |
| title | Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands |
| title_full | Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands |
| title_fullStr | Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands |
| title_full_unstemmed | Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands |
| title_short | Palladium-catalyzed Suzuki–Miyaura cross-coupling with $\alpha $-aminophosphonates based on 1,3,4-oxadiazole as ligands |
| title_sort | palladium catalyzed suzuki miyaura cross coupling with alpha aminophosphonates based on 1 3 4 oxadiazole as ligands |
| topic | $\alpha $-Aminophosphonate 1,3,4-Oxadiazole Palladium catalysis Suzuki–Miyaura cross-coupling Hemilabile ligand |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.144/ |
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