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

• Published in: Advanced materials (Weinheim) Vol. 37; no. 6; pp. e2413638 - n/a
• Main Authors: Chen, Yu, Sun, Sheng‐Nan, Chen, Xiao‐Hong, Chen, Ming‐Lin, Lin, Jiao‐Min, Niu, Qian, Li, Shun‐Li, Liu, Jiang, Lan, Ya‐Qian
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 01.02.2025
• Subjects: Cascade chemical reactions; Catalysis; Catalysts; Chemical reactions; Chemical synthesis; covalent‐organic frameworks; Cross coupling; Dehydrogenation; pharmaceutical synthesis; photocatalyst; Photosensitivity; Photosynthesis; Quinazolinones; Room temperature; covalent‐organic frameworks; photocatalyst; pharmaceutical synthesis
• ISSN: 0935-9648; 1521-4095; 1521-4095
• DOI: 10.1002/adma.202413638

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. By utilizing anthracene and metalloporphyrin as the active components for the activation of oxygen and the catalysis of intramolecular cross‐oxidation coupling reaction, respectively, a series of photosensitive and stable tandem heterogeneous COF catalysts are constructed for realizing the efficient photosynthesis of 4‐quinazolinones. Particularly, TAPP‐Cu‐An enables one‐step, gram‐scale photosynthesis of 4‐quinazolinones in a short time and under mild conditions.