Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
Nanoscale. 2023 Feb 16;15(7):3560-3565. doi: 10.1039/d2nr05825a.
Transition-metal clusters have attracted great attention in catalysis due to their unique reactivity and electronic properties, especially for novel substrate binding and activation modes at the bridging coordination sites of metal clusters. Although palladium complexes have demonstrated outstanding catalytic performance in various transformations, the catalytic behaviors of polynuclear palladium clusters in many important synthetic methodologies remain much less explored so far. Herein, we disclose the use of an atomically defined tri-nuclear palladium (PdCl) species as a catalyst precursor in Ag(I)-assisted direct C-H arylation with aryl iodides under mild conditions. This catalyst system leads to the formation of synthetically important biaryls in good yields with high site selectivities without the assistance of directing groups.
过渡金属簇由于其独特的反应性和电子性质而在催化中引起了极大的关注，特别是在金属簇的桥接配位位置上具有新型的底物结合和活化模式。尽管钯配合物在各种转化中表现出优异的催化性能，但迄今为止，多核钯簇在许多重要合成方法中的催化行为仍未得到充分探索。在此，我们公开了在温和条件下，使用原子定义的三核钯（PdCl）物种作为催化剂前体，在 Ag（I）辅助下直接进行 C-H 芳基化反应，与芳基碘反应。该催化剂体系在没有导向基团辅助的情况下，以高的位点选择性得到了具有重要合成价值的联芳烃，产率良好。
