中国科学技术大学顾振华团队报道了共面手性5H-环戊烷[2,1-b:3,4-b']联吡啶配体的合成及其在不对称开环反应中的应用。相关论文发表在2024年10月8日出版的《德国应用化学》杂志上。

联吡啶是一类配体，以其在许多过渡金属催化反应中的多功能性和有效性而闻名。手性联吡啶配体以其独特的反应性和立体选择性而闻名。

该文中，研究人员设计并合成了一类具有轴向手性支架的联吡啶配体。这些配体具有以下特征：（a）有利于金属螯合的精确排列的共面联吡啶框架；（b） 金属联吡啶配合物周围能够容纳具有大空间体积的底物的宽敞环境；（c） 由轴向手性结构引起的手性口袋。

这些手性平面联吡啶配体成功应用于铜催化的，环状二芳基碘与大体积仲胺的开环反应中，实现了之前未成功的高效和立体选择性。

附：英文原文

Title: Coplanar Atropochiral 5H-Cyclopenta[2,1-b:3,4-b']dipyridine Ligands: Synthesis and Applications in Asymmetric Ring-Opening Reaction

Author: Han Yang, Xiaojie Sun, Zhen Chen, Chenming Jiang, Longhui Duan, Jinbo Zhao, Zhenhua Gu

Issue&Volume: 2024-10-08

Abstract: Bipyridines represent a class of ligands renowned for their versatility and efficacy in numerous transition metal-catalyzed reactions. Chiral bipyridine ligands are noted for their distinctive reactivity and stereoselectivity. In this work, we have designed and synthesized a class of bipyridine ligands endowed with an axially chiral scaffold. These ligands feature: (a) a precisely aligned coplanar bipyridine framework that is beneficial for metal chelation; (b) a spacious environment around the metal-bipyridine complexes, capable of hosting substrates with substantial steric bulk; (c) a chiral pocket induced by the axially chiral architecture. These atropochiral planar bipyridine ligands were successfully applied in copper-catalyzed ring-opening reactions of cyclic diaryliodoniums with bulky secondary amines, achieving high efficiency and stereoselectivity that were unsuccessful in our previous efforts.

DOI: 10.1002/anie.202416839

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202416839