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...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2019-07-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/24/14/2628 |
| _version_ | 1818695722700111872 |
|---|---|
| author | Chuqiang Que Peipei Huang Zhanhui Yang Ning Chen Jiaxi Xu |
| author_facet | Chuqiang Que Peipei Huang Zhanhui Yang Ning Chen Jiaxi Xu |
| author_sort | Chuqiang Que |
| collection | DOAJ |
| 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-<i>N,N</i>-dimethyl-2-(<i>N,N</i>-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its <i>N</i>-phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[<i>c</i>]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(<i>N,N</i>-dialkylsulfamoyl)acetamides; and (3) for 2-diazo-<i>N</i>-phenyl-2-(<i>N</i>-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the <i>N</i>-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 <i>N</i>-aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group. |
| first_indexed | 2024-12-17T13:50:00Z |
| format | Article |
| id | doaj.art-9dc3c60993594390810c3123fc987fe9 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-12-17T13:50:00Z |
| publishDate | 2019-07-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-9dc3c60993594390810c3123fc987fe92022-12-21T21:46:04ZengMDPI AGMolecules1420-30492019-07-012414262810.3390/molecules24142628molecules24142628Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamidesChuqiang Que0Peipei Huang1Zhanhui Yang2Ning Chen3Jiaxi Xu4State Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, ChinaState Key Laboratory of Chemical Resource Engineering, Department of Organic Chemistry, College of Chemistry, Beijing University of Chemical Technology, Beijing 100029, ChinaThe 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-<i>N,N</i>-dimethyl-2-(<i>N,N</i>-diphenylsulfamoyl)acetamide can take the formal aromatic 1,5-C-H insertion in its <i>N</i>-phenylsulfonamide moiety to afford the corresponding 1,3-dihydrobenzo[<i>c</i>]isothiazole-3-carboxamide 2,2-dioxide derivative; (2) no aliphatic C-H insertions occur for 2-diazo-2-(<i>N,N</i>-dialkylsulfamoyl)acetamides; and (3) for 2-diazo-<i>N</i>-phenyl-2-(<i>N</i>-phenylsulfamoyl)acetamides, the formal aromatic 1,5-C-H insertion in the <i>N</i>-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 <i>N</i>-aryl substituents on acetamide are more active than those on sulfonamide. The chemoselectivity is controlled by electronic effect of the aryl group.https://www.mdpi.com/1420-3049/24/14/2628amidecarbene insertionC-H insertioncompetitive reactiondiazo compoundsulfonamidesultam |
| spellingShingle | Chuqiang Que Peipei Huang Zhanhui Yang Ning Chen Jiaxi Xu Intramolecular Carbene C-H Insertion Reactions of 2-Diazo-2-sulfamoylacetamides Molecules amide carbene insertion C-H insertion competitive reaction diazo compound sulfonamide sultam |
| 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 | amide carbene insertion C-H insertion competitive reaction diazo compound sulfonamide sultam |
| url | https://www.mdpi.com/1420-3049/24/14/2628 |
| work_keys_str_mv | AT chuqiangque intramolecularcarbenechinsertionreactionsof2diazo2sulfamoylacetamides AT peipeihuang intramolecularcarbenechinsertionreactionsof2diazo2sulfamoylacetamides AT zhanhuiyang intramolecularcarbenechinsertionreactionsof2diazo2sulfamoylacetamides AT ningchen intramolecularcarbenechinsertionreactionsof2diazo2sulfamoylacetamides AT jiaxixu intramolecularcarbenechinsertionreactionsof2diazo2sulfamoylacetamides |