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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 |
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author | Hashikawa, Yoshifumi Okamoto, Shu Murata, Yasujiro |
author_facet | Hashikawa, Yoshifumi Okamoto, Shu Murata, Yasujiro |
author_sort | Hashikawa, Yoshifumi |
collection | PubMed |
description | 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. |
format | Online Article Text |
id | pubmed-9814461 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-98144612023-01-10 Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene Hashikawa, Yoshifumi Okamoto, Shu Murata, Yasujiro Commun Chem Article 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. Nature Publishing Group UK 2020-07-21 /pmc/articles/PMC9814461/ /pubmed/36703330 http://dx.doi.org/10.1038/s42004-020-00340-x Text en © The Author(s) 2020 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Hashikawa, Yoshifumi Okamoto, Shu Murata, Yasujiro Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title | Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title_full | Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title_fullStr | Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title_full_unstemmed | Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title_short | Organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
title_sort | organophosphorus zwitterions engaged in a conjugated macrocycle on fullerene |
topic | Article |
url | 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 |
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