Kai Zhang, Luhai Yuan, Dexuan Cai, Xihao Tang, Ziad Alsudairy, Shengrun Zheng, Mubiao Xie, J. Fan, Yuwei Zhang, Weiguang ZHANG, Xinle Li, Songliang Cai
Introducing macropores within chiral covalent organic frameworks (COFs) offers a potent solution to the low-efficiency mass transport common in micro- and mesoporous chiral COFs. Nevertheless, this attempt remains untapped to date. Here, we report the first hierarchically macro-mesoporous chiral COF, termed macro- L -DTPC-TP, using a template-assisted approach. Through this strategy, a β-ketoenamine-linked chiral COF bearing pyrrolidine moieties was assembled around monodisperse polystyrene (PS) nanospheres (∼200 nm), during which in situ deprotection of the tert -butoxycarbonyl (Boc) group occurred. Subsequent removal of the PS template produced macro- L -DTPC-TP COF with high crystallinity, macro-mesoporous structure, and inherent chiral pyrrolidine sites. The introduction of interconnected meso- and macropores significantly improved the catalytic efficiency of COF in the aqueous asymmetric aldol reaction. Compared to the pristine mesoporous L -DTPC-TP COF (51% yield), macro- L -DTPC-TP COF exhibited a remarkably high yield of 98%, underscoring the pivotal role of macropores in enhancing mass transport and substrate accessibility. This work presents the first example of a hierarchically macro-mesoporous chiral COF and establishes macropore incorporation as an effective strategy to overcome diffusion limitations and advance the performance of COF-based asymmetric catalysis.