eGeminal-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

2023-10-26

10.1038/s41586-023-06529-z

NATURE   影响因子和分区

0028-0836

1476-4687

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis(1-4). 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 states(5,6). 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 density(8). 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.

SCI ; IC ; CCR

英语

ESI热点 ; ESI高被引

通讯

MOE Tier 2[MOE-T2EP10122-0003] ; Agency for Science, Technology and Research (A*STAR) under its MTC IRG grant["A20E5c0096","M22K2c0082"] ; Pharma Innovation Programme Singapore (PIPS, A*STAR-IAF-PP)["A19B3a0016","A20B3a0107"] ; National Natural Science Foundation of China["51825201","22033005"] ; NCCR Catalysis[180544] ; National Key RD Project["2022YFA1503900","2022YFA1503000"] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Natural Science Basic Research Program of Shaanxi["2021JCW-20","2022KJXX-18"]

Science & Technology - Other Topics

Multidisciplinary Sciences

WOS:001169105200011

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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, Inst Chem & Bioengn, Dept Chem & Appl Biosci, Zurich, Switzerland
9.Tsinghua Univ, Dept Chem, Beijing, Peoples R China
10.Tsinghua Univ, Minist Educ, Engn Res Ctr Adv Rare Earth Mat, 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. eGeminal-atom catalysis for cross-coupling[J]. NATURE,2023,622(7984).

Hai, Xiao.,Zheng, Yang.,Yu, Qi.,Guo, Na.,Xi, Shibo.,...&Lu, Jiong.(2023).eGeminal-atom catalysis for cross-coupling.NATURE,622(7984).

Hai, Xiao,et al."eGeminal-atom catalysis for cross-coupling".NATURE 622.7984(2023).