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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...

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Autores principales: Aitken, R. Alan, Harper, Andrew D., Slawin, Alexandra M. Z.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2021
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.
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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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