Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties
The successful use of 1,3,4,2-triazaphospholenes (TAPs) as organo-catalysts stresses the need for efficient synthetic routes to these molecules. In this study, we establish the [1 + 4]-cycloaddition of PBr<sub>3</sub> to azo-pyridines as a new approach to preparing pyrido-annellated TAPs...
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| Format: | Article |
| Language: | English |
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MDPI AG
2022-07-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/15/4747 |
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| author | Ferdinand Richter Nicholas Birchall Christoph M. Feil Martin Nieger Dietrich Gudat |
| author_facet | Ferdinand Richter Nicholas Birchall Christoph M. Feil Martin Nieger Dietrich Gudat |
| author_sort | Ferdinand Richter |
| collection | DOAJ |
| description | The successful use of 1,3,4,2-triazaphospholenes (TAPs) as organo-catalysts stresses the need for efficient synthetic routes to these molecules. In this study, we establish the [1 + 4]-cycloaddition of PBr<sub>3</sub> to azo-pyridines as a new approach to preparing pyrido-annellated TAPs in a single step from easily available precursors. The modular assembly of the azo-component via condensation of primary amines and nitroso compounds along with the feasibility of post-functionalization at the P–Br bond under conservation of the heterocyclic structure allows, in principle, to address a wide range of target molecules, which is illustrated by prototypical examples. The successful synthesis of a transition metal complex confirms for the first time the ability of a TAP to act as a P-donor ligand. Crystallographic studies suggest that hyperconjugation effects and intermolecular interactions induce a qualitatively similar ionic polarization of the P–Br bonds in TAPs as in better known isoelectronic diazaphospholenes. |
| first_indexed | 2024-03-09T05:11:11Z |
| format | Article |
| id | doaj.art-9210ba10b6bb404289b59e4bb69d42b5 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T05:11:11Z |
| publishDate | 2022-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-9210ba10b6bb404289b59e4bb69d42b52023-12-03T12:49:25ZengMDPI AGMolecules1420-30492022-07-012715474710.3390/molecules27154747Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand PropertiesFerdinand Richter0Nicholas Birchall1Christoph M. Feil2Martin Nieger3Dietrich Gudat4Institut für Anorganische Chemie, University of Stuttgart, 70550 Stuttgart, GermanyInstitut für Anorganische Chemie, University of Stuttgart, 70550 Stuttgart, GermanyInstitut für Anorganische Chemie, University of Stuttgart, 70550 Stuttgart, GermanyDepartment of Chemistry, University of Helsinki, FIN-00014 Helsinki, FinlandInstitut für Anorganische Chemie, University of Stuttgart, 70550 Stuttgart, GermanyThe successful use of 1,3,4,2-triazaphospholenes (TAPs) as organo-catalysts stresses the need for efficient synthetic routes to these molecules. In this study, we establish the [1 + 4]-cycloaddition of PBr<sub>3</sub> to azo-pyridines as a new approach to preparing pyrido-annellated TAPs in a single step from easily available precursors. The modular assembly of the azo-component via condensation of primary amines and nitroso compounds along with the feasibility of post-functionalization at the P–Br bond under conservation of the heterocyclic structure allows, in principle, to address a wide range of target molecules, which is illustrated by prototypical examples. The successful synthesis of a transition metal complex confirms for the first time the ability of a TAP to act as a P-donor ligand. Crystallographic studies suggest that hyperconjugation effects and intermolecular interactions induce a qualitatively similar ionic polarization of the P–Br bonds in TAPs as in better known isoelectronic diazaphospholenes.https://www.mdpi.com/1420-3049/27/15/4747phosphorus nitrogen heterocycles[1 + 4]-cycloadditionN-heterocyclic phosphinesphosphine complexesP-donor ligands |
| spellingShingle | Ferdinand Richter Nicholas Birchall Christoph M. Feil Martin Nieger Dietrich Gudat Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties Molecules phosphorus nitrogen heterocycles [1 + 4]-cycloaddition N-heterocyclic phosphines phosphine complexes P-donor ligands |
| title | Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties |
| title_full | Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties |
| title_fullStr | Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties |
| title_full_unstemmed | Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties |
| title_short | Annellated 1,3,4,2-Triazaphospholenes-Simple Modular Synthesis and a First Exploration of Ligand Properties |
| title_sort | annellated 1 3 4 2 triazaphospholenes simple modular synthesis and a first exploration of ligand properties |
| topic | phosphorus nitrogen heterocycles [1 + 4]-cycloaddition N-heterocyclic phosphines phosphine complexes P-donor ligands |
| url | https://www.mdpi.com/1420-3049/27/15/4747 |
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