Geminal-atom catalysis for cross-coupling

Hai, Xiao1; Zheng, Yang1; Yu, Qi2,3; Guo, Na4,5; Xi, Shibo6; Zhao, Xiaoxu7; Mitchell, Sharon8; Luo, Xiaohua1; Tulus, Victor8; Wang, Mu1; Sheng, Xiaoyu1; Ren, Longbin1; Long, Xiangdong1; Li, Jing1; He, Peng1; Lin, Huihui1; Cui, Yige1; Peng, Xinnan1; Shi, Jiwei1; Wu, Jie1; Zhang, Chun1,4,5; Zou, Ruqiang7; Guillen-Gosalbez, Gonzalo8; Perez-Ramirez, Javier8; Koh, Ming Joo1; Zhu, Ye1; Li, Jun9,10,11,12; Lu, Jiong1

2023-09-01

10.1038/s41586-023-06529

NATURE   Impact Factor & Quartile

0028-0836

1476-4687

["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 pi-bonding nature in a polymeric carbon nitride (PCN) host7 permit the coordination of Cu geminal sites with a ground-state separation of about 4 angstrom 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.","Heterogeneous geminal-atom catalysts, which pair single-atom sites in specific coordination and spatial proximity, offer a new avenue for the sustainable manufacture of fine chemicals."]

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English

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Corresponding

J. Lu acknowledges support from MOE Tier 2 (MOE-T2EP50121-0008) and the Agency for Science, Technology and Research (A*STAR) under its MTC IRG grant (project nos. M22K2c0082 and A20E5c0096). Y. Zhu acknowledges support from Pharma Innovation Programme Sing[MOE-T2EP10122-0003] ; MOE Tier 2[A20E5c0096] ; Agency for Science, Technology and Research (A*STAR) under its MTC IRG grant["PIPS, A*STAR-IAF-PP A19B3a0016","A20B3a0107"] ; Pharma Innovation Programme Singapore[22033005] ; National Natural Science Foundation of China[180544] ; National Centre of Competence in Research - Swiss National Science Foundation["2022YFA1503900","2022YFA1503000"] ; NSFC Center for Single-Atom Catalysis, National Key Ramp;D Project[2020B121201002] ; Guangdong Provincial Key Laboratory of Catalysis["2021JCW-20","2022KJXX-18"]

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Web of Science

1.Natl Univ Singapore, Dept Chem, Singapore, Singapore
2.Shaanxi Univ Technol, Sch Mat Sci & Engn, Hanzhong, Peoples R China
3.Shaanxi Univ Technol, Shaanxi Key Lab Catalysis, Hanzhong, Peoples R China
4.Natl Univ Singapore, Chongqing Res Inst, Chongqing, Peoples R China
5.Natl Univ Singapore, Dept Phys, Singapore, Singapore
6.ASTAR, Inst Sustainabil Chem, Energy & Environm ISCE2, Singapore, Singapore
7.Peking Univ, Sch Mat Sci & Engn, Beijing, Peoples R China
8.Swiss Fed Inst Technol, Dept Chem & Appl Biosci, Inst Chem & Bioengn, Zurich, Switzerland
9.Tsinghua Univ, Dept Chem, Beijing, Peoples R China
10.Tsinghua Univ, Engn Res Ctr Adv Rare Earth Mat, Minist Educ, Beijing, Peoples R China
11.Southern Univ Sci & Technol, Dept Chem, Shenzhen, Peoples R China
12.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalyt Chem, Shenzhen, Peoples R China

Hai, Xiao,Zheng, Yang,Yu, Qi,et al. Geminal-atom catalysis for cross-coupling[J]. NATURE,2023.

Hai, Xiao.,Zheng, Yang.,Yu, Qi.,Guo, Na.,Xi, Shibo.,...&Lu, Jiong.(2023).Geminal-atom catalysis for cross-coupling.NATURE.

Hai, Xiao,et al."Geminal-atom catalysis for cross-coupling".NATURE (2023).