Xiao Gang, Li Peifeng, Zhao Yilin, Xu Shengnan, Su Haijia
State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science, and Engineering (BAIC-SM), College of Life Science and Technology, Beijing University of Chemical Technology, No. 15, North 3rd Ring Rd East, Chaoyang District, Beijing, 100029, P.R. China.
Chem Asian J. 2018 May 20. doi: 10.1002/asia.201800515.
Green and efficient procedures are essential for the chemoselective hydrogenation of functionalized nitroarenes to form industrially important anilines. Herein, it is shown that visible-light-driven, chemoselective hydrogenation of functionalized nitroarenes with groups sensitive to forming anilines can be achieved in good to excellent yields (82-100 %) in water under relatively mild conditions and catalyzed by low-cost and recyclable graphitic carbon nitride. The process is also applicable to gram-scale reaction, with a yield of aniline of 86 %. A study of the mechanism reveals that visible-light-induced electrons are responsible for the hydrogenation reactions, and thermal energy can also promote the photocatalytic activity. A study of the kinetics shows that this reaction possibly occurs through one-step hydrogenation or stepwise condensation routes. A wide range of applications can be expected for this green, efficient, and highly selective photocatalysis system in reduction reactions for the synthesis of fine chemicals.
绿色高效的方法对于官能化硝基芳烃的化学选择性氢化以形成具有工业重要性的苯胺至关重要。在此表明，在相对温和的条件下，在水中，以低成本且可回收的石墨相氮化碳为催化剂，对于对形成苯胺敏感的官能化硝基芳烃，可见光驱动的化学选择性氢化能够以良好至优异的产率（82 - 100%）实现。该过程也适用于克级反应，苯胺产率为86%。机理研究表明，可见光诱导的电子负责氢化反应，并且热能也能促进光催化活性。动力学研究表明，该反应可能通过一步氢化或逐步缩合途径发生。这种绿色、高效且高度选择性的光催化体系在精细化学品合成的还原反应中有望得到广泛应用。
