Yang Lei, Zhang Yan-Ping, You Yong, Wang Zhen-Hua, Yuan Wei-Cheng, Zhao Jian-Qiang
Innovation Research Center of Chiral Drugs, Institute for Advanced Study, Chengdu University, Chengdu, 610106, China.
Chem Rec. 2025 Jul;25(7):e202500085. doi: 10.1002/tcr.202500085. Epub 2025 May 29.
Macrocyclophanes are a class of macrocyclic molecules featuring aliphatic ansa chains linking non-adjacent positions of an aromatic ring, which have garnered significant attention due to their extensive applications in biological activity, pharmaceutical research, and selective optical recognition. In this review, it summarizes recent advancements in the catalytic enantioselective synthesis of planar-chiral macrocyclophanes, focusing on various synthetic routes, including: a) transition-metal-catalyzed enantioselective alkyne cyclotrimerization for planar construction; b) (dynamic) kinetic resolution of achiral or prochiral macrocyclophanes; c) enantioselective substitution of aromatic rings; and d) enantioselective macrocyclization for the formation of ansa chains. The aim is to highlight the state-of-the-art advances in catalytic enantioselective construction of planar-chiral macrocyclophanes and to push this field toward new horizons.
大环环芳是一类大环分子，其特征在于脂肪族桥链连接芳环的非相邻位置，由于它们在生物活性、药物研究和选择性光学识别方面的广泛应用而备受关注。在这篇综述中，总结了平面手性大环环芳催化对映选择性合成的最新进展，重点介绍了各种合成路线，包括：a）过渡金属催化的对映选择性炔烃环三聚反应以构建平面结构；b）非手性或前手性大环环芳的（动态）动力学拆分；c）芳环的对映选择性取代；d）对映选择性大环化以形成桥链。目的是突出平面手性大环环芳催化对映选择性构建的最新进展，并推动该领域迈向新的高度。
