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Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides
The intramolecular C-H insertions of carbenes derived from 2-diazo-2-sulfamoylacetamides were studied. 2-Diazo-2-sulfamoylacetamides were first prepared from chloroacetyl chloride and secondary amines through acylation followed by sequential treatments with sodium sulfite, phosphorus oxychloride, se...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6680402/ https://www.ncbi.nlm.nih.gov/pubmed/31330952 http://dx.doi.org/10.3390/molecules24142628 |
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author | Que, Chuqiang Huang, Peipei Yang, Zhanhui Chen, Ning Xu, Jiaxi |
author_facet | Que, Chuqiang Huang, Peipei Yang, Zhanhui Chen, Ning Xu, Jiaxi |
author_sort | Que, Chuqiang |
collection | PubMed |
description | The intramolecular C-H insertions of carbenes derived from 2-diazo-2-sulfamoylacetamides were studied. 2-Diazo-2-sulfamoylacetamides were first prepared from chloroacetyl chloride and secondary amines through acylation followed by sequential treatments with sodium sulfite, phosphorus oxychloride, secondary amines, and 4-nitrobenzenesulfonyl azide. The results indicate that: (1) 2-diazo-N,N-dimethyl-2-(N,N-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its N-phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[c]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(N,N-dialkylsulfamoyl)acetamides; and (3) for 2-diazo-N-phenyl-2-(N-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the N-phenylacetamide moiety is favorable to afford the corresponding 3-sulfamoylindolin-2-one derivatives as sole or major products. The intramolecular competitive aromatic 1,5-C-H insertion reactions of 2-diazo-2-sulfamoylacetamides with aryl groups on both amide and sulfonamide groups reveal that the N-aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group. |
format | Online Article Text |
id | pubmed-6680402 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-66804022019-08-09 Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides Que, Chuqiang Huang, Peipei Yang, Zhanhui Chen, Ning Xu, Jiaxi Molecules Article The intramolecular C-H insertions of carbenes derived from 2-diazo-2-sulfamoylacetamides were studied. 2-Diazo-2-sulfamoylacetamides were first prepared from chloroacetyl chloride and secondary amines through acylation followed by sequential treatments with sodium sulfite, phosphorus oxychloride, secondary amines, and 4-nitrobenzenesulfonyl azide. The results indicate that: (1) 2-diazo-N,N-dimethyl-2-(N,N-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its N-phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[c]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(N,N-dialkylsulfamoyl)acetamides; and (3) for 2-diazo-N-phenyl-2-(N-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the N-phenylacetamide moiety is favorable to afford the corresponding 3-sulfamoylindolin-2-one derivatives as sole or major products. The intramolecular competitive aromatic 1,5-C-H insertion reactions of 2-diazo-2-sulfamoylacetamides with aryl groups on both amide and sulfonamide groups reveal that the N-aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group. MDPI 2019-07-19 /pmc/articles/PMC6680402/ /pubmed/31330952 http://dx.doi.org/10.3390/molecules24142628 Text en © 2019 by the authors. 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 (http://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Que, Chuqiang Huang, Peipei Yang, Zhanhui Chen, Ning Xu, Jiaxi Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title | Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title_full | Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title_fullStr | Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title_full_unstemmed | Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title_short | Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides |
title_sort | intramolecular carbene c-h insertion reactions of 2-diazo-2-sulfamoylacetamides |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6680402/ https://www.ncbi.nlm.nih.gov/pubmed/31330952 http://dx.doi.org/10.3390/molecules24142628 |
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