Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds
The food industry generates vast amounts of waste and one of the most abundant is the biopolymer chitin, which is the main constituent of crustacean shells and insect exoskeletons. The alkaline deacetylation of the N-acetyl-d-glucosamino units of chitin leads to chitosan, a stable, inexpensive, non-...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-01-01
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| Series: | Tetrahedron Green Chem |
| Subjects: | |
| Online Access: | http://www.sciencedirect.com/science/article/pii/S2773223123000055 |
| _version_ | 1827275517087186944 |
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| author | Gabriela M. Diogo Pedro A.M. Moro Taíssa A. Costin Mariane Fantinel Marcus M. Sá |
| author_facet | Gabriela M. Diogo Pedro A.M. Moro Taíssa A. Costin Mariane Fantinel Marcus M. Sá |
| author_sort | Gabriela M. Diogo |
| collection | DOAJ |
| description | The food industry generates vast amounts of waste and one of the most abundant is the biopolymer chitin, which is the main constituent of crustacean shells and insect exoskeletons. The alkaline deacetylation of the N-acetyl-d-glucosamino units of chitin leads to chitosan, a stable, inexpensive, non-toxic, biocompatible, and biodegradable material of basic properties due to the presence of free amino groups. In the present study, we report the catalytic activity of commercially available chitosan as a sustainable heterogeneous catalyst for the preparation of α-diazo carbonyl compounds through the diazo transfer reaction to active methylene compounds using a sulfonyl azide as the diazo transfer reagent. Thus, 17 α-diazo carbonyl compounds were readily prepared under mild conditions in 50–92% yield after a simple work-up consisting of vacuum filtration to separate the insoluble catalyst and the sulfonamide byproduct. This procedure was also adapted to aqueous medium, making the process more environmentally benign. The recovery and recyclability of the biocatalyst were also addressed, with the catalytic activity being slightly reduced after four reuses depending on the substrate used. The synthetic potential of diazo carbonyl compounds was further demonstrated through the rhodium-catalyzed O–H insertion reactions. |
| first_indexed | 2024-03-08T10:28:13Z |
| format | Article |
| id | doaj.art-11768aa36b04424991a30b8e94fec733 |
| institution | Directory Open Access Journal |
| issn | 2773-2231 |
| language | English |
| last_indexed | 2025-03-22T06:42:09Z |
| publishDate | 2023-01-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Tetrahedron Green Chem |
| spelling | doaj.art-11768aa36b04424991a30b8e94fec7332024-04-24T04:52:15ZengElsevierTetrahedron Green Chem2773-22312023-01-011100006Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compoundsGabriela M. Diogo0Pedro A.M. Moro1Taíssa A. Costin2Mariane Fantinel3Marcus M. Sá4Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900, BrazilDepartamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900, BrazilDepartamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900, BrazilDepartamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900, BrazilCorresponding author.; Departamento de Química, Universidade Federal de Santa Catarina, Florianópolis, SC, 88040-900, BrazilThe food industry generates vast amounts of waste and one of the most abundant is the biopolymer chitin, which is the main constituent of crustacean shells and insect exoskeletons. The alkaline deacetylation of the N-acetyl-d-glucosamino units of chitin leads to chitosan, a stable, inexpensive, non-toxic, biocompatible, and biodegradable material of basic properties due to the presence of free amino groups. In the present study, we report the catalytic activity of commercially available chitosan as a sustainable heterogeneous catalyst for the preparation of α-diazo carbonyl compounds through the diazo transfer reaction to active methylene compounds using a sulfonyl azide as the diazo transfer reagent. Thus, 17 α-diazo carbonyl compounds were readily prepared under mild conditions in 50–92% yield after a simple work-up consisting of vacuum filtration to separate the insoluble catalyst and the sulfonamide byproduct. This procedure was also adapted to aqueous medium, making the process more environmentally benign. The recovery and recyclability of the biocatalyst were also addressed, with the catalytic activity being slightly reduced after four reuses depending on the substrate used. The synthetic potential of diazo carbonyl compounds was further demonstrated through the rhodium-catalyzed O–H insertion reactions.http://www.sciencedirect.com/science/article/pii/S2773223123000055Chitosanα-diazo carbonyl compoundsHeterogeneous catalysisGreen chemistry |
| spellingShingle | Gabriela M. Diogo Pedro A.M. Moro Taíssa A. Costin Mariane Fantinel Marcus M. Sá Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds Tetrahedron Green Chem Chitosan α-diazo carbonyl compounds Heterogeneous catalysis Green chemistry |
| title | Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds |
| title_full | Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds |
| title_fullStr | Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds |
| title_full_unstemmed | Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds |
| title_short | Chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α-diazo carbonyl compounds |
| title_sort | chitosan as a sustainable heterogeneous catalyst for the preparation of functionalized α diazo carbonyl compounds |
| topic | Chitosan α-diazo carbonyl compounds Heterogeneous catalysis Green chemistry |
| url | http://www.sciencedirect.com/science/article/pii/S2773223123000055 |
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