Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins
Abstract Allylic amide moieties are commonly encountered in natural products and are privileged structures in pharmaceuticals and agrochemicals. Moreover, because allylic amide can be to converted into an array of high‐value motifs, they have been widely employed in organic synthesis. However, the d...
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Wiley
2025-01-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202411744 |
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| author | Xiaoyang Fu Jiarui Tian Mingjun Zhang Yue Jing Yuxiu Liu Hongjian Song Qingmin Wang |
| author_facet | Xiaoyang Fu Jiarui Tian Mingjun Zhang Yue Jing Yuxiu Liu Hongjian Song Qingmin Wang |
| author_sort | Xiaoyang Fu |
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| description | Abstract Allylic amide moieties are commonly encountered in natural products and are privileged structures in pharmaceuticals and agrochemicals. Moreover, because allylic amide can be to converted into an array of high‐value motifs, they have been widely employed in organic synthesis. However, the development of catalytic systems for intermolecular allylic amidation of olefins, particularly branched α‐olefins, has proven to be challenging. Here, a biomimetic, synergistic catalytic method is reported that combines photoredox, cobalt, and Brønsted base catalysis for the synthesis of substituted allylic amides from branched α‐olefins and simple imides without using oxidants. This low‐cost, operationally simple method features a broad substrate scope and excellent functional group compatibility. Moreover, it is successfully used for the functionalization of several structurally complex molecules demonstrating the method's potential utility for medicinal chemistry applications. Mechanistic studies revealed that C(sp3)─N bond formation is mediated by a nitrogen‐centered radical intermediate, which is generated via a sequence involving deprotonation and single‐electron oxidation. |
| format | Article |
| id | doaj-art-0bafc7bf98e042fdb8fe47034a913064 |
| institution | Kabale University |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-0bafc7bf98e042fdb8fe47034a9130642025-01-13T15:29:43ZengWileyAdvanced Science2198-38442025-01-01122n/an/a10.1002/advs.202411744Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐OlefinsXiaoyang Fu0Jiarui Tian1Mingjun Zhang2Yue Jing3Yuxiu Liu4Hongjian Song5Qingmin Wang6State Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaState Key Laboratory of Elemento‐Organic Chemistry Research Institute of Elemento‐Organic Chemistry Frontiers Science Center for New Organic Matter College of Chemistry Nankai University Tianjin 300071 P. R. ChinaAbstract Allylic amide moieties are commonly encountered in natural products and are privileged structures in pharmaceuticals and agrochemicals. Moreover, because allylic amide can be to converted into an array of high‐value motifs, they have been widely employed in organic synthesis. However, the development of catalytic systems for intermolecular allylic amidation of olefins, particularly branched α‐olefins, has proven to be challenging. Here, a biomimetic, synergistic catalytic method is reported that combines photoredox, cobalt, and Brønsted base catalysis for the synthesis of substituted allylic amides from branched α‐olefins and simple imides without using oxidants. This low‐cost, operationally simple method features a broad substrate scope and excellent functional group compatibility. Moreover, it is successfully used for the functionalization of several structurally complex molecules demonstrating the method's potential utility for medicinal chemistry applications. Mechanistic studies revealed that C(sp3)─N bond formation is mediated by a nitrogen‐centered radical intermediate, which is generated via a sequence involving deprotonation and single‐electron oxidation.https://doi.org/10.1002/advs.202411744allylic amidebiomimetic catalysisbranched α‐olefincobaloximesphotochemistry |
| spellingShingle | Xiaoyang Fu Jiarui Tian Mingjun Zhang Yue Jing Yuxiu Liu Hongjian Song Qingmin Wang Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins Advanced Science allylic amide biomimetic catalysis branched α‐olefin cobaloximes photochemistry |
| title | Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins |
| title_full | Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins |
| title_fullStr | Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins |
| title_full_unstemmed | Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins |
| title_short | Biomimetic Dehydrogenative Intermolecular Formal Allylic Amidation of Branched α‐Olefins |
| title_sort | biomimetic dehydrogenative intermolecular formal allylic amidation of branched α olefins |
| topic | allylic amide biomimetic catalysis branched α‐olefin cobaloximes photochemistry |
| url | https://doi.org/10.1002/advs.202411744 |
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