Hu Xueqing, Zhao Yunxu, He Tong, Niu Caoyue, Liu Feipeng, Jia Wei, Mu Yi, Li Xingwei, Rong Zi-Qiang
Frontiers Science Center for Flexible Electronics (FSCFE), Shaanxi Institute of Flexible Electronics (SIFE), Northwestern Polytechnical University (NPU) Xi'an 710072 China
School of Chemistry and Chemical Engineering, Shaanxi Normal University (SNNU) Xi'an 710119 China
Chem Sci. 2024 Jul 22;15(33):13541-13549. doi: 10.1039/d4sc01837k. eCollection 2024 Aug 22.
Distal biaxial atropisomers are typical structures in chiral catalysts and ligands and offer a wide variety of applications in biology and materials technology, but the development of efficient synthesis of these valuable scaffolds is still in great demand. Herein, we describe a highly efficient iridium catalyzed asymmetric C-H alkylation reaction that provides a range of new distal biaxial atropisomers with excellent yields (up to 99%) and stereoselectivity (up to 99% ee and essentially one isomer). Based on this unprecedented strategy, a polycyclic skeleton with five successive chiral centers as well as C-C and C-N (or N-N) two distal chiral axes was created successfully in mild circumstances. In addition, the optically pure products bearing fluorophores show circular polarized luminescence (CPL) properties, being potential candidate materials for CPL applications.
远端双轴阻转异构体是手性催化剂和配体中的典型结构,在生物学和材料技术中有广泛的应用,但高效合成这些有价值的骨架结构仍有很大需求。在此,我们描述了一种高效的铱催化不对称C-H烷基化反应,该反应能以优异的产率(高达99%)和立体选择性(高达99% ee且基本上为单一异构体)提供一系列新型远端双轴阻转异构体。基于这一前所未有的策略,成功地在温和条件下构建了一个具有五个连续手性中心以及C-C和C-N(或N-N)两条远端手性轴的多环骨架。此外,带有荧光团的光学纯产物表现出圆偏振发光(CPL)特性,是CPL应用的潜在候选材料。