Predesign of Covalent‐Organic Frameworks for Efficient Photocatalytic Dehydrogenative Cross‐Coupling Reaction

The dehydrogenative cross-coupling reaction is the premier route for synthesizing important 4-quinazolinone drugs. However, it usually requires high reaction temperature and long reaction time, and the yield of the final product is low. Here two stable and photosensitive covalent-organic frameworks (COFs), TAPP-An and TAPP-Cu-An are purposefully designed and constructed to serve as unprecedented heterogeneous tandem catalysts to complete dehydrogenative cross-coupling reactions in a short time and under mild reaction conditions (room temperature and light), leading to the high-efficient photosynthesis of 4-quinazolinones. Particularly, TAPP-Cu-An is the best heterogeneous catalyst currently available for the synthesis of 4-quinazolinones, even surpassing all the catalysts reported so far. It also enables one-step photosynthesis of 4-quinazolinones with higher conversion (>99%) and selectivity (>99%) in a shorter time, and the product can be easily prepared on a gram scale. Extensive experiments combined with theoretical calculations show that the excellent photogenerated charge separation and transport capability, as well as the synergistic An-Cu catalysis in TAPP-Cu-An are the main driving forces for this efficient reaction.