Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles
Abstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplor...
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Wiley
2024-01-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202306728 |
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| author | Yang Xie Ruilong Zhang Ze‐Le Chen Mengtao Rong Hui He Shaofei Ni Xiang‐Kui He Wen‐Jing Xiao Jun Xuan |
| author_facet | Yang Xie Ruilong Zhang Ze‐Le Chen Mengtao Rong Hui He Shaofei Ni Xiang‐Kui He Wen‐Jing Xiao Jun Xuan |
| author_sort | Yang Xie |
| collection | DOAJ |
| description | Abstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base–boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research. |
| first_indexed | 2024-03-08T13:00:39Z |
| format | Article |
| id | doaj.art-bc0e2451f657446684c708097251407b |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-03-08T13:00:39Z |
| publishDate | 2024-01-01 |
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| series | Advanced Science |
| spelling | doaj.art-bc0e2451f657446684c708097251407b2024-01-19T09:27:54ZengWileyAdvanced Science2198-38442024-01-01113n/an/a10.1002/advs.202306728Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled PyrazolesYang Xie0Ruilong Zhang1Ze‐Le Chen2Mengtao Rong3Hui He4Shaofei Ni5Xiang‐Kui He6Wen‐Jing Xiao7Jun Xuan8Anhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province College of Chemistry & Chemical Engineering Anhui University Hefei Anhui 230601 P. R. ChinaAnhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province College of Chemistry & Chemical Engineering Anhui University Hefei Anhui 230601 P. R. ChinaAnhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province College of Chemistry & Chemical Engineering Anhui University Hefei Anhui 230601 P. R. ChinaAnhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province College of Chemistry & Chemical Engineering Anhui University Hefei Anhui 230601 P. R. ChinaDepartment of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province Shantou University Shantou Guangdong 515063 P. R. ChinaDepartment of Chemistry and Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province Shantou University Shantou Guangdong 515063 P. R. ChinaKey Laboratory of Pesticide and Chemical Biology Ministry of Education College of Chemistry Central China Normal University Wuhan Hubei 430079 P. R. ChinaKey Laboratory of Pesticide and Chemical Biology Ministry of Education College of Chemistry Central China Normal University Wuhan Hubei 430079 P. R. ChinaAnhui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials and Key Laboratory of Functional Inorganic Materials of Anhui Province College of Chemistry & Chemical Engineering Anhui University Hefei Anhui 230601 P. R. ChinaAbstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base–boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research.https://doi.org/10.1002/advs.202306728cascade radical cyclizationheterocycle synthesisphotochemistryreaction mechanismsvinyldiazo reagents |
| spellingShingle | Yang Xie Ruilong Zhang Ze‐Le Chen Mengtao Rong Hui He Shaofei Ni Xiang‐Kui He Wen‐Jing Xiao Jun Xuan Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles Advanced Science cascade radical cyclization heterocycle synthesis photochemistry reaction mechanisms vinyldiazo reagents |
| title | Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles |
| title_full | Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles |
| title_fullStr | Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles |
| title_full_unstemmed | Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles |
| title_short | Photocatalytic Boryl Radicals Triggered Sequential B─N/C─N Bond Formation to Assemble Boron‐Handled Pyrazoles |
| title_sort | photocatalytic boryl radicals triggered sequential b─n c─n bond formation to assemble boron handled pyrazoles |
| topic | cascade radical cyclization heterocycle synthesis photochemistry reaction mechanisms vinyldiazo reagents |
| url | https://doi.org/10.1002/advs.202306728 |
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