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Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene
Organophosphorus zwitterions are one of the most important but elusive intermediates for carbon–carbon bond formation in synthetic chemistry and biology. However, a lack of isolated examples due to their lability has hampered in-depth understanding of structures and their reaction mechanisms. In thi...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9814461/ https://www.ncbi.nlm.nih.gov/pubmed/36703330 http://dx.doi.org/10.1038/s42004-020-00340-x |
Sumario: | Organophosphorus zwitterions are one of the most important but elusive intermediates for carbon–carbon bond formation in synthetic chemistry and biology. However, a lack of isolated examples due to their lability has hampered in-depth understanding of structures and their reaction mechanisms. In this study, we crystallographically reveal the solid-state structure of a phosha-Michael adduct engaged in a cage-opened C(60) skeleton, which is formed as a kinetic product. This compound exhibits dark brown colour in solution with an intense absorption band that extends to 1000 nm, reflecting intramolecular charge transfer transitions. From the 1,2-dicarbonyl moiety on the conjugated orifice, β-oxo-phosphorus ylide is formed as a thermodynamic product. The reaction mechanism that has long been disputed is examined by experimental and theoretical studies, showing a pathway which includes an S(N)2 reaction as a key step instead of the hitherto considered carbene pathway. |
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