Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base
Three isomeric (benzyloxythienyl)oxazolines <b>9</b>, <b>11</b> and <b>13</b> 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 gi...
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| Format: | Article |
| Language: | English |
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MDPI AG
2021-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/24/7690 |
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| author | R. Alan Aitken Andrew D. Harper Alexandra M. Z. Slawin |
| author_facet | R. Alan Aitken Andrew D. Harper Alexandra M. Z. Slawin |
| author_sort | R. Alan Aitken |
| collection | DOAJ |
| description | Three isomeric (benzyloxythienyl)oxazolines <b>9</b>, <b>11</b> and <b>13</b> 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 <b>11</b> leading to exclusive Wittig rearrangement, the shortest distance in <b>13</b> giving exclusively cyclisation-derived products, and the intermediate distance in <b>9</b> leading to both processes being observed. The corresponding <i>N</i>-butyl amides were also obtained in two cases and one of these undergoes efficient Wittig rearrangement leading to a thieno[2,3-<i>c</i>]pyrrolone product. |
| first_indexed | 2024-03-10T03:28:08Z |
| format | Article |
| id | doaj.art-3fb607dfbb07415aa434853ba526a63e |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T03:28:08Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-3fb607dfbb07415aa434853ba526a63e2023-11-23T09:47:54ZengMDPI AGMolecules1420-30492021-12-012624769010.3390/molecules26247690Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a BaseR. Alan Aitken0Andrew D. Harper1Alexandra M. Z. Slawin2EaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, Fife, UKEaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, Fife, UKEaStCHEM School of Chemistry, University of St Andrews, North Haugh, St Andrews KY16 9ST, Fife, UKThree isomeric (benzyloxythienyl)oxazolines <b>9</b>, <b>11</b> and <b>13</b> 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 <b>11</b> leading to exclusive Wittig rearrangement, the shortest distance in <b>13</b> giving exclusively cyclisation-derived products, and the intermediate distance in <b>9</b> leading to both processes being observed. The corresponding <i>N</i>-butyl amides were also obtained in two cases and one of these undergoes efficient Wittig rearrangement leading to a thieno[2,3-<i>c</i>]pyrrolone product.https://www.mdpi.com/1420-3049/26/24/7690oxazolineWittig rearrangementthiophenethieno[2,3-<i>c</i>]pyrroloneX-ray structure |
| spellingShingle | R. Alan Aitken Andrew D. Harper Alexandra M. Z. Slawin Rationalisation of Patterns of Competing Reactivity by X-ray Structure Determination: Reaction of Isomeric (Benzyloxythienyl)oxazolines with a Base Molecules oxazoline Wittig rearrangement thiophene thieno[2,3-<i>c</i>]pyrrolone X-ray structure |
| 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 | oxazoline Wittig rearrangement thiophene thieno[2,3-<i>c</i>]pyrrolone X-ray structure |
| url | https://www.mdpi.com/1420-3049/26/24/7690 |
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