Geminal-atom catalysis for cross-coupling

Xiao Hai, Yang Zheng, Qi Yu, Na Guo, Shibo Xi (), Xiaoxu Zhao, Sharon Mitchell, Xiaohua Luo, Victor Tulus, Mu Wang, Xiaoyu Sheng, Longbin Ren, Xiangdong Long, Jing Li, Peng He, Huihui Lin, Yige Cui, Xinnan Peng, Jiwei Shi, Jie Wu, Chun Zhang, Ruqiang Zou, Gonzalo Guillén-Gosálbez, Javier Pérez-Ramírez (), Ming Joo Koh (), Ye Zhu (), Jun Li () and Jiong Lu ()
Additional contact information
Xiao Hai: National University of Singapore
Yang Zheng: National University of Singapore
Qi Yu: Shaanxi University of Technology
Na Guo: National University of Singapore (Chongqing) Research Institute
Shibo Xi: Agency for Science, Technology and Research (A*STAR)
Xiaoxu Zhao: Peking University
Sharon Mitchell: ETH Zurich
Xiaohua Luo: National University of Singapore
Victor Tulus: ETH Zurich
Mu Wang: National University of Singapore
Xiaoyu Sheng: National University of Singapore
Longbin Ren: National University of Singapore
Xiangdong Long: National University of Singapore
Jing Li: National University of Singapore
Peng He: National University of Singapore
Huihui Lin: National University of Singapore
Yige Cui: National University of Singapore
Xinnan Peng: National University of Singapore
Jiwei Shi: National University of Singapore
Jie Wu: National University of Singapore
Chun Zhang: National University of Singapore
Ruqiang Zou: Peking University
Gonzalo Guillén-Gosálbez: ETH Zurich
Javier Pérez-Ramírez: ETH Zurich
Ming Joo Koh: National University of Singapore
Ye Zhu: National University of Singapore
Jun Li: Tsinghua University
Jiong Lu: National University of Singapore

Nature, 2023, vol. 622, issue 7984, 754-760

Abstract: Abstract Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis1–4. However, the architecture of these mononuclear metal species stabilized on solid supports may not be optimal for catalysing complex molecular transformations owing to restricted spatial environment and electronic quantum states5,6. Here we report a class of heterogeneous geminal-atom catalysts (GACs), which pair single-atom sites in specific coordination and spatial proximity. Regularly separated nitrogen anchoring groups with delocalized π-bonding nature in a polymeric carbon nitride (PCN) host7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density8. The adaptable coordination of individual Cu sites in GACs enables a cooperative bridge-coupling pathway through dynamic Cu–Cu bonding for diverse C–X (X = C, N, O, S) cross-couplings with a low activation barrier. In situ characterization and quantum-theoretical studies show that such a dynamic process for cross-coupling is triggered by the adsorption of two different reactants at geminal metal sites, rendering homo-coupling unfeasible. These intrinsic advantages of GACs enable the assembly of heterocycles with several coordination sites, sterically congested scaffolds and pharmaceuticals with highly specific and stable activity. Scale-up experiments and translation to continuous flow suggest broad applicability for the manufacturing of fine chemicals.

Date: 2023
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DOI: 10.1038/s41586-023-06529-z

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