Phosphine-catalyzed vinylation at low acetylene pressure
The vinylation of various nucleophiles with acetylene at a maximum pressure of 1.5 bar is achieved by organocatalysis with easily accessible phosphines like tri-nbutylphosphine. A detailed mechanistic investigation by quantum-chemical and experimental methods supports a nucleophilic activation of ac...
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| Hauptverfasser: | , , , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
2021
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| In: |
The journal of organic chemistry
Year: 2021, Jahrgang: 86, Heft: 18, Pages: 13041-13055 |
| ISSN: | 1520-6904 |
| DOI: | 10.1021/acs.joc.1c01807 |
| Online-Zugang: | Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.joc.1c01807 Verlag, lizenzpflichtig, Volltext: https://pubs.acs.org/doi/10.1021/acs.joc.1c01807 
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| Verfasserangaben: | Nikolai A. Sitte, Maximilian Menche, Pavel Tužina, Frank Bienewald, Ansgar Schäfer, Peter Comba, Frank Rominger, A. Stephen K. Hashmi and Thomas Schaub |
| Zusammenfassung: | The vinylation of various nucleophiles with acetylene at a maximum pressure of 1.5 bar is achieved by organocatalysis with easily accessible phosphines like tri-nbutylphosphine. A detailed mechanistic investigation by quantum-chemical and experimental methods supports a nucleophilic activation of acetylene by the phosphine catalyst. At 140 °C and typically 5 mol % catalyst loading, cyclic amides, oxazolidinones, ureas, unsaturated cyclic amines, and alcohols were successfully vinylated. Furthermore, the in situ generation of a vinyl phosphonium species can also be utilized in Wittig-type functionalization of aldehydes. |
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| Beschreibung: | Gesehen am 15.11.2021 |
| Beschreibung: | Online Resource |
| ISSN: | 1520-6904 |
| DOI: | 10.1021/acs.joc.1c01807 |