Synthesis of Naphthylpyridines from Unsymmetrical Naphthylheptadiynes and the Configurational Stability of the Biaryl Axis
A series of different unsymmetrically substituted naphthyl-based diynes were synthesized. These substrates formed the foundation for the assembly of novel biaryls containing pyridine moieties with differently substituted five-membered rings in the backbone of the newly formed heterobiaryl system. Th...
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| Hauptverfasser: | , , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
March 21, 2016
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| In: |
The journal of organic chemistry
Year: 2016, Jahrgang: 81, Heft: 8, Pages: 3087-3102 |
| ISSN: | 1520-6904 |
| DOI: | 10.1021/acs.joc.5b02190 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.joc.5b02190
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| Verfasserangaben: | Fabian Fischer, Alexander F. Siegle, Marek Checinski, Christine Fischer, Karolin Kral, Richard Thede, Oliver Trapp, Marko Hapke |
| Zusammenfassung: | A series of different unsymmetrically substituted naphthyl-based diynes were synthesized. These substrates formed the foundation for the assembly of novel biaryls containing pyridine moieties with differently substituted five-membered rings in the backbone of the newly formed heterobiaryl system. The key step for their efficient construction was the photo- and cobalt-catalyzed [2 + 2 + 2] cycloaddition reaction between the corresponding naphthyldiyne and aceto- or benzonitrile. The heterobiaryl products have been isolated and investigated with respect to the configurational stability of their biaryl axis using dynamic chiral HPLC; subtle effects of the substitution pattern on the stability of the axis were observed. For several compounds the activation barriers (ΔG‡) of racemization were determined. Suitable substitution of the five-membered ring backbone exemplarily allowed the Co-catalyzed enantioselective cyclization to yield the enantiomerically enriched heterobiaryl. |
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| Beschreibung: | Gesehen am 19.05.2020 |
| Beschreibung: | Online Resource |
| ISSN: | 1520-6904 |
| DOI: | 10.1021/acs.joc.5b02190 |