Guo Xiaojun, Jia Xinyu, He Qin, Duan Wengui, Zhang Yanjun, Huang Yan, Liu Luzhi
School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China.
Guangxi Key Laboratory of Green Chemical Materials and Safety Technology, Guangxi Engineering Research Center for New Chemical Materials and Safety Technology, College of Petroleum and Chemical Engineering, Beibu Gulf University, Qinzhou 535011, China.
Molecules. 2025 Mar 28;30(7):1517. doi: 10.3390/molecules30071517.
Seeking a supramolecular chiral system induced by trace chiral molecules instead of traditional complex and expensive chiral ligands to achieve high yield or ee value conversion of the products is of great significance in asymmetric synthesis but still remains a challenge. Herein, two types of double helical supramolecular chiral systems, ()- and ()-, with opposite chiral optics were constructed in situ using tyrosine-functionalized pillar[5]arene as inducers. These systems exhibit chiroptical stability and enable remarkable chirality amplification from 7 mol% chiral seeds. When applied to intermolecular olefin cyano-trifluoromethylation, ()- exhibits remarkable catalytic efficiency (yield up to 89%), whereas ()- achieves higher enantioselectivity (ee up to 84%). This research will provide new ideas for supramolecular chiral catalysts in organic asymmetric catalysis applications.
寻求由痕量手性分子诱导而非传统复杂且昂贵的手性配体诱导的超分子手性体系，以实现产物的高收率或对映体过量值转化，在不对称合成中具有重要意义，但仍然是一项挑战。在此，使用酪氨酸功能化的柱[5]芳烃作为诱导剂原位构建了两种具有相反手性光学的双螺旋超分子手性体系，即（）-和（）-。这些体系表现出手性光学稳定性，并能从7 mol%的手性种子实现显著的手性放大。当应用于分子间烯烃氰基-三氟甲基化反应时，（）-表现出显著的催化效率（收率高达89%），而（）-则实现了更高的对映选择性（对映体过量高达84%）。本研究将为超分子手性催化剂在有机不对称催化应用中提供新思路。
