An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes
The new polynucleating tripodal proligand $\text{H}_6\text{tren(dpa)}_3$, containing thirteen nitrogen donors of four different types, was designed, synthesized, and isolated in good yield (${\sim }$60%) via a transition-metal-free triple N-arylation of $\text{H}_6$tren with HXdpa (X $=$ Br or F), u...
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Académie des sciences
2023-03-01
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| Series: | Comptes Rendus. Chimie |
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| Online Access: | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.223/ |
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| author | Nicolini, Alessio Anderlini, Biagio Roncaglia, Fabrizio Cornia, Andrea |
| author_facet | Nicolini, Alessio Anderlini, Biagio Roncaglia, Fabrizio Cornia, Andrea |
| author_sort | Nicolini, Alessio |
| collection | DOAJ |
| description | The new polynucleating tripodal proligand $\text{H}_6\text{tren(dpa)}_3$, containing thirteen nitrogen donors of four different types, was designed, synthesized, and isolated in good yield (${\sim }$60%) via a transition-metal-free triple N-arylation of $\text{H}_6$tren with HXdpa (X $=$ Br or F), using $\text{K}_2\text{CO}_3$ or $\text{Cs}_2\text{CO}_3$ as a base ($\text{H}_6$tren $=$ tris(2-aminoethyl)amine, HXdpa $=$ 6-halogeno-$N$-(pyridin-2-yl)pyridin-2-amine). HFdpa was prepared with excellent yield (90–92%) by reaction of 2,6-difluoropyridine with 2-aminopyridine in LiH/toluene/pyridine and was found more reactive than HBrdpa, affording higher conversion and higher yield. Use of $\text{Cs}_2\text{CO}_3$ turned out to be essential for achieving high regioselectivity and eliminating overarylation almost completely. |
| format | Article |
| id | doaj-art-ffbb019bb85844e0bea7fb62fe349239 |
| institution | Kabale University |
| issn | 1878-1543 |
| language | English |
| publishDate | 2023-03-01 |
| publisher | Académie des sciences |
| record_format | Article |
| series | Comptes Rendus. Chimie |
| spelling | doaj-art-ffbb019bb85844e0bea7fb62fe3492392025-02-07T13:38:00ZengAcadémie des sciencesComptes Rendus. Chimie1878-15432023-03-0126G1516210.5802/crchim.22310.5802/crchim.223An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenesNicolini, Alessio0https://orcid.org/0000-0002-4742-5458Anderlini, Biagio1https://orcid.org/0000-0003-4641-3137Roncaglia, Fabrizio2https://orcid.org/0000-0001-7630-4375Cornia, Andrea3https://orcid.org/0000-0001-9765-3128Department of Chemical and Geological Sciences, University of Modena and Reggio Emilia & INSTM, I-41125 Modena, ItalyDepartment of Chemical and Geological Sciences, University of Modena and Reggio Emilia & INSTM, I-41125 Modena, ItalyDepartment of Chemical and Geological Sciences, University of Modena and Reggio Emilia & INSTM, I-41125 Modena, ItalyDepartment of Chemical and Geological Sciences, University of Modena and Reggio Emilia & INSTM, I-41125 Modena, ItalyThe new polynucleating tripodal proligand $\text{H}_6\text{tren(dpa)}_3$, containing thirteen nitrogen donors of four different types, was designed, synthesized, and isolated in good yield (${\sim }$60%) via a transition-metal-free triple N-arylation of $\text{H}_6$tren with HXdpa (X $=$ Br or F), using $\text{K}_2\text{CO}_3$ or $\text{Cs}_2\text{CO}_3$ as a base ($\text{H}_6$tren $=$ tris(2-aminoethyl)amine, HXdpa $=$ 6-halogeno-$N$-(pyridin-2-yl)pyridin-2-amine). HFdpa was prepared with excellent yield (90–92%) by reaction of 2,6-difluoropyridine with 2-aminopyridine in LiH/toluene/pyridine and was found more reactive than HBrdpa, affording higher conversion and higher yield. Use of $\text{Cs}_2\text{CO}_3$ turned out to be essential for achieving high regioselectivity and eliminating overarylation almost completely.https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.223/Oligo-$\alpha $-pyridylamidesTripodal ligandsHalopyridinesMetal-freeBuchwald–HartwigEMACs |
| spellingShingle | Nicolini, Alessio Anderlini, Biagio Roncaglia, Fabrizio Cornia, Andrea An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes Comptes Rendus. Chimie Oligo-$\alpha $-pyridylamides Tripodal ligands Halopyridines Metal-free Buchwald–Hartwig EMACs |
| title | An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes |
| title_full | An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes |
| title_fullStr | An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes |
| title_full_unstemmed | An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes |
| title_short | An efficient transition-metal-free route to oligo-$\alpha $-pyridylamines via fluoroarenes |
| title_sort | efficient transition metal free route to oligo alpha pyridylamines via fluoroarenes |
| topic | Oligo-$\alpha $-pyridylamides Tripodal ligands Halopyridines Metal-free Buchwald–Hartwig EMACs |
| url | https://comptes-rendus.academie-sciences.fr/chimie/articles/10.5802/crchim.223/ |
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