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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...

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Autores principales: Hashikawa, Yoshifumi, Okamoto, Shu, Murata, Yasujiro
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Nature Publishing Group UK 2020
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.
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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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