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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...

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Detalles Bibliográficos
Autores principales: Que, Chuqiang, Huang, Peipei, Yang, Zhanhui, Chen, Ning, Xu, Jiaxi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: MDPI 2019
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.
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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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