Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents
Abstract As an ambident nucleophile, controlling the reaction selectivities of nitrogen and oxygen atoms in amide moiety is a challenging issue in organic synthesis. Herein, we present a chemodivergent cycloisomerization approach to construct isoquinolinone and iminoisocoumarin skeletons from o-alke...
| Main Authors: | , , , |
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2023-06-01
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| Series: | Communications Chemistry |
| Online Access: | https://doi.org/10.1038/s42004-023-00930-5 |
| _version_ | 1797801500187033600 |
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| author | Jiaxin He Feng-Huan Du Chi Zhang Yunfei Du |
| author_facet | Jiaxin He Feng-Huan Du Chi Zhang Yunfei Du |
| author_sort | Jiaxin He |
| collection | DOAJ |
| description | Abstract As an ambident nucleophile, controlling the reaction selectivities of nitrogen and oxygen atoms in amide moiety is a challenging issue in organic synthesis. Herein, we present a chemodivergent cycloisomerization approach to construct isoquinolinone and iminoisocoumarin skeletons from o-alkenylbenzamide derivatives. The chemo-controllable strategy employed an exclusive 1,2-aryl migration/elimination cascade, enabled by different hypervalent iodine species generated in situ from the reaction of iodosobenzene (PhIO) with MeOH or 2,4,6-tris-isopropylbenzene sulfonic acid. DFT studies revealed that the nitrogen and oxygen atoms of the intermediates in the two reaction systems have different nucleophilicities and thus produce the selectivity of N or O-attack modes. |
| first_indexed | 2024-03-13T04:52:18Z |
| format | Article |
| id | doaj.art-565b202d57ed48499add484c1b4297b9 |
| institution | Directory Open Access Journal |
| issn | 2399-3669 |
| language | English |
| last_indexed | 2024-03-13T04:52:18Z |
| publishDate | 2023-06-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Communications Chemistry |
| spelling | doaj.art-565b202d57ed48499add484c1b4297b92023-06-18T11:08:44ZengNature PortfolioCommunications Chemistry2399-36692023-06-01611910.1038/s42004-023-00930-5Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagentsJiaxin He0Feng-Huan Du1Chi Zhang2Yunfei Du3Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin UniversityState Key Laboratory of Elemento-Organic Chemistry, The Research Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityState Key Laboratory of Elemento-Organic Chemistry, The Research Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai UniversityTianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology, Tianjin UniversityAbstract As an ambident nucleophile, controlling the reaction selectivities of nitrogen and oxygen atoms in amide moiety is a challenging issue in organic synthesis. Herein, we present a chemodivergent cycloisomerization approach to construct isoquinolinone and iminoisocoumarin skeletons from o-alkenylbenzamide derivatives. The chemo-controllable strategy employed an exclusive 1,2-aryl migration/elimination cascade, enabled by different hypervalent iodine species generated in situ from the reaction of iodosobenzene (PhIO) with MeOH or 2,4,6-tris-isopropylbenzene sulfonic acid. DFT studies revealed that the nitrogen and oxygen atoms of the intermediates in the two reaction systems have different nucleophilicities and thus produce the selectivity of N or O-attack modes.https://doi.org/10.1038/s42004-023-00930-5 |
| spellingShingle | Jiaxin He Feng-Huan Du Chi Zhang Yunfei Du Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents Communications Chemistry |
| title | Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents |
| title_full | Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents |
| title_fullStr | Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents |
| title_full_unstemmed | Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents |
| title_short | Chemoselective cycloisomerization of O-alkenylbenzamides via concomitant 1,2-aryl migration/elimination mediated by hypervalent iodine reagents |
| title_sort | chemoselective cycloisomerization of o alkenylbenzamides via concomitant 1 2 aryl migration elimination mediated by hypervalent iodine reagents |
| url | https://doi.org/10.1038/s42004-023-00930-5 |
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