Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts
Abstract Heterogeneous single-atom catalysts (SACs) have gained significant attention for their maximized atom utilization and well-defined active sites, but they often struggle with multi-stage organic cross-coupling reactions due to limited coordination space and reactivity. Here, we report an “an...
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Nature Portfolio
2025-04-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-58579-8 |
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| author | Jiwei Shi Gang Wang Duanshuai Tian Xiao Hai Rongwei Meng Yifan Xu Yu Teng Lu Ma Shibo Xi Youqing Yang Xin Zhou Xingjie Fu Hengyu Li Qilong Cai Peng He Huihui Lin Jinxing Chen Jiali Li Jinghan Li Qian He Quan-Hong Yang Jun Li Dongshuang Wu Yang-Gang Wang Jie Wu Jiong Lu |
| author_facet | Jiwei Shi Gang Wang Duanshuai Tian Xiao Hai Rongwei Meng Yifan Xu Yu Teng Lu Ma Shibo Xi Youqing Yang Xin Zhou Xingjie Fu Hengyu Li Qilong Cai Peng He Huihui Lin Jinxing Chen Jiali Li Jinghan Li Qian He Quan-Hong Yang Jun Li Dongshuang Wu Yang-Gang Wang Jie Wu Jiong Lu |
| author_sort | Jiwei Shi |
| collection | DOAJ |
| description | Abstract Heterogeneous single-atom catalysts (SACs) have gained significant attention for their maximized atom utilization and well-defined active sites, but they often struggle with multi-stage organic cross-coupling reactions due to limited coordination space and reactivity. Here, we report an “anchoring-borrowing” strategy combined facet engineering to develop artful single-atom catalysts (ASACs) through anchoring foreign single atoms onto specific facets of the non-innocent reducible carriers. ASACs exhibit adaptive coordination, effectively bypassing the oxidative-addition prerequisite for bivalent elevation at a single metal site in both homogenous and heterogeneous cross-couplings. For example, Pd1-CeO2(110) ASAC exhibits unparalleled activity in coupling with more accessible aryl chlorides, and challenging heterocycles, outperforming traditional catalysts with a remarkable turnover number of 45,327,037. Mechanistic studies reveal that ASACs leverage dynamic structural changes, with reducible carriers acting as electron reservoirs, significantly lowering reaction barriers. Furthermore, ASACs enable efficient synthesis of biologically significant compounds, drug intermediates, and active pharmaceutical ingredients (APIs) through a scalable high-speed circulated flow synthesis, underscoring great potential for sustainable fine chemical manufacturing. |
| format | Article |
| id | doaj-art-daa0f895f39748a3985609abc069f52b |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-daa0f895f39748a3985609abc069f52b2025-08-20T03:07:43ZengNature PortfolioNature Communications2041-17232025-04-0116111210.1038/s41467-025-58579-8Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalystsJiwei Shi0Gang Wang1Duanshuai Tian2Xiao Hai3Rongwei Meng4Yifan Xu5Yu Teng6Lu Ma7Shibo Xi8Youqing Yang9Xin Zhou10Xingjie Fu11Hengyu Li12Qilong Cai13Peng He14Huihui Lin15Jinxing Chen16Jiali Li17Jinghan Li18Qian He19Quan-Hong Yang20Jun Li21Dongshuang Wu22Yang-Gang Wang23Jie Wu24Jiong Lu25Department of Chemistry, National University of SingaporeDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, ShenzhenDepartment of Chemistry, National University of SingaporeSchool of Materials Science and Engineering, Peking UniversityDepartment of Chemistry, National University of SingaporeSchool of Materials and Engineering, Nanyang Technological UniversityDepartment of Chemistry, National University of SingaporeNational Synchrotron Light Source II Brookhaven National Lab UptonInstitute of Sustainability for Chemicals, Energy and Environment (ISCE2), Agency for Science, Technology and Research (A*STAR), 1 Pesek Road Jurong IslandDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeSchool of Environmental Science and Engineering, Suzhou University of Science and TechnologyDepartment of Material Science and Engineering, College of Design and Engineering, National University ofJoint School of National University of Singapore and Tianjin University, International Campus of Tianjin University, Binhai New CityDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, ShenzhenSchool of Materials and Engineering, Nanyang Technological UniversityDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, ShenzhenDepartment of Chemistry, National University of SingaporeDepartment of Chemistry, National University of SingaporeAbstract Heterogeneous single-atom catalysts (SACs) have gained significant attention for their maximized atom utilization and well-defined active sites, but they often struggle with multi-stage organic cross-coupling reactions due to limited coordination space and reactivity. Here, we report an “anchoring-borrowing” strategy combined facet engineering to develop artful single-atom catalysts (ASACs) through anchoring foreign single atoms onto specific facets of the non-innocent reducible carriers. ASACs exhibit adaptive coordination, effectively bypassing the oxidative-addition prerequisite for bivalent elevation at a single metal site in both homogenous and heterogeneous cross-couplings. For example, Pd1-CeO2(110) ASAC exhibits unparalleled activity in coupling with more accessible aryl chlorides, and challenging heterocycles, outperforming traditional catalysts with a remarkable turnover number of 45,327,037. Mechanistic studies reveal that ASACs leverage dynamic structural changes, with reducible carriers acting as electron reservoirs, significantly lowering reaction barriers. Furthermore, ASACs enable efficient synthesis of biologically significant compounds, drug intermediates, and active pharmaceutical ingredients (APIs) through a scalable high-speed circulated flow synthesis, underscoring great potential for sustainable fine chemical manufacturing.https://doi.org/10.1038/s41467-025-58579-8 |
| spellingShingle | Jiwei Shi Gang Wang Duanshuai Tian Xiao Hai Rongwei Meng Yifan Xu Yu Teng Lu Ma Shibo Xi Youqing Yang Xin Zhou Xingjie Fu Hengyu Li Qilong Cai Peng He Huihui Lin Jinxing Chen Jiali Li Jinghan Li Qian He Quan-Hong Yang Jun Li Dongshuang Wu Yang-Gang Wang Jie Wu Jiong Lu Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts Nature Communications |
| title | Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts |
| title_full | Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts |
| title_fullStr | Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts |
| title_full_unstemmed | Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts |
| title_short | Defying the oxidative-addition prerequisite in cross-coupling through artful single-atom catalysts |
| title_sort | defying the oxidative addition prerequisite in cross coupling through artful single atom catalysts |
| url | https://doi.org/10.1038/s41467-025-58579-8 |
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