近日，郑州大学於兵团队报道了新开发的Pd/ZU-Phos/DBN协同催化能够实现对映选择性[4+2]环化，有效合成各种螺环支架。相关论文于2025年10月20日发表在《国家科学评论》杂志上。

手性配体在不对称催化中具有重要的应用价值，因为它极大地提高了催化过程的化学选择性。多个配体的协同作用可以通过优化催化循环中的单个步骤来提高催化效率和选择性。

研究组合成了一系列新的P-手性配体 (ZU-Phos)，使1,2-二取代的烯丙基碳酸酯与活化的烯烃形成高效的不对称[4 + 2]环，通过一种新的双配位机制，产生了各种具有光学活性和药用价值的螺旋环支架，其产率高达96%和98% ee。机制研究表明，DBN具有Br形成独特的混合连接Pd/ZU-Phos/DBN配合物。

研究组强调了Pd/ZU-Phos配体催化的独特优势，并强调了双配体体系在扩大钯催化反应范围方面的功效。密度泛函理论（DFT）计算表明，DBN通过弱配位调节钯催化剂的催化活性，并通过与磷配体的弱相互作用稳定手性环境，增强产物对映选择性。

附：英文原文

Title: Newly developed Pd/ZU-Phos/DBN cooperative catalysis enables enantioselective [4 + 2] annulations for efficient synthesis of diverse spirocyclic scaffolds

Author: Shi, Linlin, Guo, Mengyan, Xu, Mengya, Li, Er-Qing, Chang, Junbiao, Yu, Bin

Issue&Volume: 2025-10-20

Abstract: Chiral ligands are essential for asymmetric catalysis as they greatly improve the chemical selectivity of the catalytic process. The cooperative action of multiple ligands may enhance catalytic efficiency and selectivity by optimizing individual steps within the catalytic cycle. Here, we synthesized a series of novel P-chiral ligands (ZU-Phos) that enabled highly efficient asymmetric [4 + 2] annulations of 1,2-disubstituted allylic carbonates with activated olefins, yielding a variety of optically active and medicinally relevant spirocyclic scaffolds with yields up to 96% and up to 98% ee through a novel dual coordination mechanism. Mechanistic investigations disclosed that DBN served a dual function as a Brnsted base and formed a unique mixed-ligated Pd/ZU-Phos/DBN complex. This study highlighted the distinctive benefits of Pd/ZU-Phos ligand catalysis and underscored the efficacy of the dual ligand system in broadening the scope of palladium-catalyzed reactions. Density functional theory (DFT) calculations showcased that DBN modulated the catalytic activity of palladium catalysts via weak coordination and enhanced product enantioselectivity by stabilizing the chiral environment through weak interactions with phosphorus ligands.

DOI: 10.1093/nsr/nwaf443

Source: https://academic.oup.com/nsr/advance-article/doi/10.1093/nsr/nwaf443/8293240searchresult=1