Direct synthesis, postsynthetic modification, and chiral induction have been recognized as three powerful methods to synthesize chiral covalent organic frameworks (CCOFs). However, catalytic asymmetric methodology, as the most important and effective synthetic approach to access chiral organics, has not been enabled for CCOFs synthesis thus far. Herein we report, for the first time, the construction of CCOFs from prochiral monomers via catalytic asymmetric polymerization. The obtained propargylamine-linked CCOFs can be the highly reusable chiral catalysts to promote asymmetric Michael addition reactions. The concept of catalytic asymmetric polymerization might open a new route for constructing the CCOFs that are not possible with the existing CCOF synthetic methods.

A COF-based phase transfer catalyst and its continuous flow-through reactor was prepared. The obtained Pd@COF-QA can highly promote the Suzuki–Miyaura coupling reaction in water under mild conditions even at gram scale level.

Although chiral covalent organic frameworks (CCOFs) presence grows in thermal asymmetric catalysis, their application in equally important asymmetric photocatalysis has yet to begin. Herein, we first report a propargylamine-linked and quaternary ammonium bromide decorated porphyrin-CCOF which can highly promote visible-light-driven enantioselective photooxidation of sulfides to sulfoxides in water and in air. This methodology has also been applied to the synthesis of (R)modafinil, a wakefulness-promoting medication used for the treatment of excessive sleepiness. This research might open a new way for the application of CCOFs in asymmetric photocatalysis.

A novel covalent organic framework material COF-DM, which contains chelating coordination environments, was synthesized at the gram level under mild conditions. In addition, its Cu­(II)-loaded complex of Cu­(II)@COF-DM was prepared by impregnating COF-DM in an acetonitrile solution of CuCl2 via a solid-state coordination approach. The obtained Cu­(II)-loaded Cu­(II)@COF-DM can be used as a highly active heterogeneous catalyst to catalyze the alkyne-dihalomethane-amine coupling reactions.

A chiral ionic liquid (CIL) moiety of a Lpyrrolidin-2-ylimidazole-decorated homochiral UiO-68-type metal−organic framework, UiO-68-CIL (1), was successfully prepared by the combination of a new premodified chiral CIL ligand (H 2 L-CIL) and ZrCl 4 via a solvothermal method. The TiO 2 -loaded TiO 2 @UiO-68-CIL (2) was prepared by impregnating 1 in a toluene solution of Ti(OPr i ) 4 and sequential in situ hydrolysis. The obtained 2 can be a bifunctional asymmetric heterogeneous catalyst to successfully promote the one-pot Morita−Baylis−Hillman reaction starting from aromatic alcohols in a tandem way.