Hai, X., Zheng, Y., Yu, Q. et al. Geminal-atom catalysis for cross-coupling. Nature 622, 754–760 (2023).
Abstract:
Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis. 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. 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) host permit the coordination of Cu geminal sites with a ground-state separation of about 4 Å at high metal density. 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.
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Funding Info:
This research / project is supported by the Agency for Science, Technology and Research (A*STAR) - Low Carbon Energy Research Finding Initiative (LCERFI01-0033 | U2102d2006)
Grant Reference no. : U2102d2006
This research / project is supported by the Ministry of Education - Academic Research Fund Tier 2
Grant Reference no. : MOE-T2EP50121-0008, MOE-T2EP10122-0003
This research / project is supported by the A*STAR - Manufacturing, Trade, and Connectivity Individual Research Grant
Grant Reference no. : M22K2c0082, A20E5c0096
This research / project is supported by the A*STAR - Industry Alignment Fund - Pre-Positioning
Grant Reference no. : A19B3a0016, A20B3a0107
Description:
This is a post-peer-review, pre-copyedit version of an article published in Nature. The final authenticated version is available online at: http://dx.doi.org/10.1038/s41586-023-06529-z