ファインケミカルと医薬品のグリーン生産のための新規触媒(Novel catalyst for green production of fine chemicals and pharmaceuticals)

2023-10-11 シンガポール国立大学(NUS)

<関連情報>

• https://news.nus.edu.sg/novel-catalyst-for-green-production-of-fine-chemicals-and-pharmaceuticals/
• https://www.nature.com/articles/s41586-023-06529-z

クロスカップリングのためのジェミナル原子触媒作用 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 & Jiong Lu

Nature  Published:20 September 2023

DOI:https://doi.org/10.1038/s41586-023-06529-z

Abstract

Single-atom catalysts (SACs) have well-defined active sites, making them of potential interest for organic synthesis^1,2,3,4. 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 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.