(Thio)urea-Based Covalent Organic Framework as a Hydrogen-Bond-Donating Catalyst.

Two-dimensional urea- and thiourea-containing covalent organic frameworks (COFs) were synthesized at ambient conditions at large scale within 1 h in the absence of an acid catalyst. The site-isolated urea and thiourea in the COF showed enhanced catalytic efficiency as a hydrogen-bond-donating organocatalyst compared to the molecular counterparts in epoxide ring-opening reaction, aldehyde acetalization, and Friedel-Crafts reaction. The COF catalysts also had excellent recyclability.