Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction
Summary: A series of heterogeneous catalysts anchored to different polystyrene-based supports has been prepared and applied in an asymmetric [2,3]-Wittig rearrangement reaction of cyclohexanone derivatives. Among them, primary amino acid-derived (aminomethylated)polystyrene-supported catalysts showe...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Elsevier
2023-10-01
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| Series: | iScience |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2589004223018990 |
| _version_ | 1797647823773106176 |
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| author | Aleksandra Murre Valdek Mikli Kristin Erkman Tõnis Kanger |
| author_facet | Aleksandra Murre Valdek Mikli Kristin Erkman Tõnis Kanger |
| author_sort | Aleksandra Murre |
| collection | DOAJ |
| description | Summary: A series of heterogeneous catalysts anchored to different polystyrene-based supports has been prepared and applied in an asymmetric [2,3]-Wittig rearrangement reaction of cyclohexanone derivatives. Among them, primary amino acid-derived (aminomethylated)polystyrene-supported catalysts showed excellent reactivity leading to the formation of rearranged products in good enantioselectivities of both diastereomers. Reusability issues connected to the deactivation of the catalyst were proved to be dependent on the end-capping strategy chosen for the blocking of the unreacted active sites of the resin. This issue of end-capping has not previously been in focus. Using bulkier pivaloyl end-capping moiety, we were able to recycle the catalyst in six consecutive cycles with only marginal deceleration of the reaction. Moreover, the epimerization of the product that occurred while conducting a rearrangement reaction in the presence of a homogeneous catalyst was almost fully eliminated by switching the catalytic system to heterogeneous. |
| first_indexed | 2024-03-11T15:23:09Z |
| format | Article |
| id | doaj.art-6e5503a19a2c4b77b77cc2788fe91049 |
| institution | Directory Open Access Journal |
| issn | 2589-0042 |
| language | English |
| last_indexed | 2024-03-11T15:23:09Z |
| publishDate | 2023-10-01 |
| publisher | Elsevier |
| record_format | Article |
| series | iScience |
| spelling | doaj.art-6e5503a19a2c4b77b77cc2788fe910492023-10-28T05:08:38ZengElsevieriScience2589-00422023-10-012610107822Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reactionAleksandra Murre0Valdek Mikli1Kristin Erkman2Tõnis Kanger3Department of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaDepartment of Materials and Environmental Technology, Tallinn University of Technology, Ehitajate tee 5, 19086 Tallinn, EstoniaDepartment of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, EstoniaDepartment of Chemistry and Biotechnology, Tallinn University of Technology, Akadeemia tee 15, 12618 Tallinn, Estonia; Corresponding authorSummary: A series of heterogeneous catalysts anchored to different polystyrene-based supports has been prepared and applied in an asymmetric [2,3]-Wittig rearrangement reaction of cyclohexanone derivatives. Among them, primary amino acid-derived (aminomethylated)polystyrene-supported catalysts showed excellent reactivity leading to the formation of rearranged products in good enantioselectivities of both diastereomers. Reusability issues connected to the deactivation of the catalyst were proved to be dependent on the end-capping strategy chosen for the blocking of the unreacted active sites of the resin. This issue of end-capping has not previously been in focus. Using bulkier pivaloyl end-capping moiety, we were able to recycle the catalyst in six consecutive cycles with only marginal deceleration of the reaction. Moreover, the epimerization of the product that occurred while conducting a rearrangement reaction in the presence of a homogeneous catalyst was almost fully eliminated by switching the catalytic system to heterogeneous.http://www.sciencedirect.com/science/article/pii/S2589004223018990Organic chemistry |
| spellingShingle | Aleksandra Murre Valdek Mikli Kristin Erkman Tõnis Kanger Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction iScience Organic chemistry |
| title | Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction |
| title_full | Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction |
| title_fullStr | Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction |
| title_full_unstemmed | Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction |
| title_short | Primary amines as heterogeneous catalysts in an enantioselective [2,3]-Wittig rearrangement reaction |
| title_sort | primary amines as heterogeneous catalysts in an enantioselective 2 3 wittig rearrangement reaction |
| topic | Organic chemistry |
| url | http://www.sciencedirect.com/science/article/pii/S2589004223018990 |
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