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Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base
Three isomeric (benzyloxythienyl)oxazolines 9, 11 and 13 have been prepared and are found, upon treatment with a strong base, to undergo either Wittig rearrangement or intramolecular attack of the benzylic anion on the oxazoline function to give products derived from cleavage of the initially formed...
Autores principales: | , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2021
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8705950/ https://www.ncbi.nlm.nih.gov/pubmed/34946776 http://dx.doi.org/10.3390/molecules26247690 |
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author | Aitken, R. Alan Harper, Andrew D. Slawin, Alexandra M. Z. |
author_facet | Aitken, R. Alan Harper, Andrew D. Slawin, Alexandra M. Z. |
author_sort | Aitken, R. Alan |
collection | PubMed |
description | Three isomeric (benzyloxythienyl)oxazolines 9, 11 and 13 have been prepared and are found, upon treatment with a strong base, to undergo either Wittig rearrangement or intramolecular attack of the benzylic anion on the oxazoline function to give products derived from cleavage of the initially formed 3-aminothienofuran products. This pattern of reactivity is directly linked to the distance between the two reactive groups as determined by X-ray diffraction, with the greatest distance in 11 leading to exclusive Wittig rearrangement, the shortest distance in 13 giving exclusively cyclisation-derived products, and the intermediate distance in 9 leading to both processes being observed. The corresponding N-butyl amides were also obtained in two cases and one of these undergoes efficient Wittig rearrangement leading to a thieno[2,3-c]pyrrolone product. |
format | Online Article Text |
id | pubmed-8705950 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2021 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-87059502021-12-25 Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base Aitken, R. Alan Harper, Andrew D. Slawin, Alexandra M. Z. Molecules Article Three isomeric (benzyloxythienyl)oxazolines 9, 11 and 13 have been prepared and are found, upon treatment with a strong base, to undergo either Wittig rearrangement or intramolecular attack of the benzylic anion on the oxazoline function to give products derived from cleavage of the initially formed 3-aminothienofuran products. This pattern of reactivity is directly linked to the distance between the two reactive groups as determined by X-ray diffraction, with the greatest distance in 11 leading to exclusive Wittig rearrangement, the shortest distance in 13 giving exclusively cyclisation-derived products, and the intermediate distance in 9 leading to both processes being observed. The corresponding N-butyl amides were also obtained in two cases and one of these undergoes efficient Wittig rearrangement leading to a thieno[2,3-c]pyrrolone product. MDPI 2021-12-20 /pmc/articles/PMC8705950/ /pubmed/34946776 http://dx.doi.org/10.3390/molecules26247690 Text en © 2021 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 Aitken, R. Alan Harper, Andrew D. Slawin, Alexandra M. Z. Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title | Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title_full | Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title_fullStr | Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title_full_unstemmed | Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title_short | Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base |
title_sort | rationalisation of patterns of competing reactivity by x-ray structure determination: reaction of isomeric (benzyloxythienyl)oxazolines with a base |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8705950/ https://www.ncbi.nlm.nih.gov/pubmed/34946776 http://dx.doi.org/10.3390/molecules26247690 |
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