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Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies

The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurizati...

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Autores principales: Ramazanova, Kyzgaldak, Müller, Anna Karina, Lönnecke, Peter, Hollóczki, Oldamur, Kirchner, Barbara, Hey-Hawkins, Evamarie
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2023
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10609391/
https://www.ncbi.nlm.nih.gov/pubmed/37894642
http://dx.doi.org/10.3390/molecules28207163
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author Ramazanova, Kyzgaldak
Müller, Anna Karina
Lönnecke, Peter
Hollóczki, Oldamur
Kirchner, Barbara
Hey-Hawkins, Evamarie
author_facet Ramazanova, Kyzgaldak
Müller, Anna Karina
Lönnecke, Peter
Hollóczki, Oldamur
Kirchner, Barbara
Hey-Hawkins, Evamarie
author_sort Ramazanova, Kyzgaldak
collection PubMed
description The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurization of the phosphorus atom, thus efficiently blocking the lone pair of electrons, as exemplified for 6b yielding structurally characterized 8b. Additionally, the influence of the substituent in the α position to the phosphorus atom (H, Ph, 2-py, CN) on the reversibility of the reaction was studied. Extensive theoretical calculations for understanding the ring-closing mechanism suggested that a multi-step reaction with one or more intermediates was most probable.
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spelling pubmed-106093912023-10-28 Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies Ramazanova, Kyzgaldak Müller, Anna Karina Lönnecke, Peter Hollóczki, Oldamur Kirchner, Barbara Hey-Hawkins, Evamarie Molecules Article The reactive P-N bond in 1-phospha-2-azanorbornenes is readily cleaved by simple alcohols to afford P-chiral 2,3-dihydrophosphole derivatives as a racemic mixture. The isolation of the products was not possible due to the reversibility of the reaction, which could, however, be stopped by sulfurization of the phosphorus atom, thus efficiently blocking the lone pair of electrons, as exemplified for 6b yielding structurally characterized 8b. Additionally, the influence of the substituent in the α position to the phosphorus atom (H, Ph, 2-py, CN) on the reversibility of the reaction was studied. Extensive theoretical calculations for understanding the ring-closing mechanism suggested that a multi-step reaction with one or more intermediates was most probable. MDPI 2023-10-19 /pmc/articles/PMC10609391/ /pubmed/37894642 http://dx.doi.org/10.3390/molecules28207163 Text en © 2023 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Article
Ramazanova, Kyzgaldak
Müller, Anna Karina
Lönnecke, Peter
Hollóczki, Oldamur
Kirchner, Barbara
Hey-Hawkins, Evamarie
Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title_full Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title_fullStr Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title_full_unstemmed Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title_short Ring-Opening Reaction of 1-Phospha-2-Azanorbornenes via P-N Bond Cleavage and Reversibility Studies
title_sort ring-opening reaction of 1-phospha-2-azanorbornenes via p-n bond cleavage and reversibility studies
topic Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10609391/
https://www.ncbi.nlm.nih.gov/pubmed/37894642
http://dx.doi.org/10.3390/molecules28207163
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