郑州大学张文静团队报道C2对称手性TPy-BPI-Pincer配体的模块化合成，及其在不对称Ni（II）催化傅克烷基化反应中的应用。相关研究成果发表在2024年12月17日出版的《中国化学》。

三吡啶配体因其在催化中丰富的配位化学，而被用作一类独特的配体。

该文中，研究人员开发了一类新的C2对称手性三吡啶吡咯并咪唑酮配体（TPy-BPI）。研究人员在吲哚与2,3-二氧代吡咯烷的不对称傅克烷基化反应中，评估了它们的催化活性。在温和条件下，对于各种底物，可以获得优异的收率（高达92%）和高对映选择性（高达97%ee）。

除了2,3-二氧代吡咯烷外，β，γ-不饱和α-酮酯在Ni（OTf）2-TPy-BPI配体L1催化的反应中也是相容的。对照实验、两个TPy-BPI L1-Ni(OTf)₂配合物的单晶结构和DFT计算，揭示了对映选择性的起源。该研究首次表明，三联吡啶骨架仅含有两个与金属配位的氮原子，额外的吡啶单元仅充当立体定向元件。这与之前报道的三联吡啶配体不同，之前报道的含有所有三个与金属配合的氮原子。

附：英文原文

Title: Modular Synthesis of C2-Symmetric Chiral TPy-BPI Pincer Ligands and Application in Asymmetric Ni(II)-Catalysed Friedel-Crafts Alkylation

Author: Hong-Xing Cen, Li-Ping Ding, Lin-Lu Liu, Wei-Dong Pan, Xian-Qiao Zhu, Wu-Wu Li, Wen-Jing Zhang, Li-Jun Peng, Xiong-Li Liu

Issue&Volume: 2024-12-17

Abstract: Terpyridine ligands have been applied as a class of unique ligands due to their rich coordination chemistry in the catalysis. Herein, we developed a new class of C2-symmetric chiral terpyridine-pyrroloimidazolone ligands (TPy-BPI). Their catalytic activity was evaluated in the asymmetric Friedel-Crafts alkylation of indoles with 2,3-dioxopyrrolidines. Excellent yields (up to 92%) and high enantioselectivities (up to 97% ee) are obtained for a wide range of substrates under mild conditions. In addition to 2,3-dioxopyrrolidines, β,γ-unsaturated α-ketoesters were also compatible in the Ni(OTf)2-TPy-BPI ligand L1-catalyzed reaction. Control experiments, single crystal structure of two TPy-BPI L1-Ni(OTf)2 complexes, and DFT calculations revealed the origins of the enantioselectivity. To the best of our knowledge, our work is the first report showing that the terpyridine framework contained only two nitrogen atoms coordinating with the metal, and the additional pyridine unit only acted as stereodirecting element, which is different from the previously reported terpyridine ligands containing all three nitrogen atoms coordinating with the metal.

DOI: 10.1002/cjoc.202400988

Source: https://onlinelibrary.wiley.com/doi/full/10.1002/cjoc.202400988