Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system
Abstract Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C–H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-01-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-56230-0 |
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| author | Le Wang Yuan She Jie Xiao Zi-Hao Li Shen-Yuan Zhang Peng-Fei Lian Tong-Mei Ding Shu-Yu Zhang |
| author_facet | Le Wang Yuan She Jie Xiao Zi-Hao Li Shen-Yuan Zhang Peng-Fei Lian Tong-Mei Ding Shu-Yu Zhang |
| author_sort | Le Wang |
| collection | DOAJ |
| description | Abstract Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C–H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji–Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C–H oxidation. Key advances include the use of a Cu/Azodiformate catalyst system to facilitate remote allylic C–H activation and the achievement of excellent chemoselectivity through a dynamic ligand exchange strategy using a bis(sulfonamide) ligand. This method features a broad substrate scope and functional group tolerance, successfully applied to the synthesis of various challenging medium-sized cyclic ethers (7-10 members) and large-ring lactones (14-20 members), with high regioselectivity and stereoselectivity. |
| format | Article |
| id | doaj-art-5560627dc6ed4c64a6d0fd74dded0193 |
| institution | Kabale University |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-5560627dc6ed4c64a6d0fd74dded01932025-01-26T12:41:59ZengNature PortfolioNature Communications2041-17232025-01-011611910.1038/s41467-025-56230-0Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst systemLe Wang0Yuan She1Jie Xiao2Zi-Hao Li3Shen-Yuan Zhang4Peng-Fei Lian5Tong-Mei Ding6Shu-Yu Zhang7Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityShanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong UniversityAbstract Allylic ethers and alcohols are essential structural motifs commonly present in natural products and pharmaceuticals. Direct allylic C–H oxygenation of internal alkenes is one of the most direct methods, bypassing the necessity for an allylic leaving group that is needed in the traditional Tsuji–Trost reaction. Herein, we develop an efficient and practical method for synthesizing (E)-allyl ethers from readily available internal alkenes and alcohols or phenols via selective allylic C–H oxidation. Key advances include the use of a Cu/Azodiformate catalyst system to facilitate remote allylic C–H activation and the achievement of excellent chemoselectivity through a dynamic ligand exchange strategy using a bis(sulfonamide) ligand. This method features a broad substrate scope and functional group tolerance, successfully applied to the synthesis of various challenging medium-sized cyclic ethers (7-10 members) and large-ring lactones (14-20 members), with high regioselectivity and stereoselectivity.https://doi.org/10.1038/s41467-025-56230-0 |
| spellingShingle | Le Wang Yuan She Jie Xiao Zi-Hao Li Shen-Yuan Zhang Peng-Fei Lian Tong-Mei Ding Shu-Yu Zhang Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system Nature Communications |
| title | Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system |
| title_full | Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system |
| title_fullStr | Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system |
| title_full_unstemmed | Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system |
| title_short | Allylic C–H oxygenation of unactivated internal olefins by the Cu/azodiformate catalyst system |
| title_sort | allylic c h oxygenation of unactivated internal olefins by the cu azodiformate catalyst system |
| url | https://doi.org/10.1038/s41467-025-56230-0 |
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