摘要
Baeyer-Villiger(BV)反应是有机化学合成中的一个重要反应.特别是催化型的BV反应不仅能够简化反应过程还能够降低反应物的消耗量和减少副产物的生成量,因此更加具有实际应用价值.其中最为有利的催化型BV反应是使用低成本、环境友好的过氧化氢(H_2O_2)作为氧化剂,来取代传统的氧化剂过酸.本综述首先简要阐述了以H_2O_2为氧化剂的BV氧化反应的特点以及传统使用的氧化剂类型,然后重点综述了Sn基催化剂材料在以H_2O_2为氧化剂的催化型BV反应中的催化性能以及相应的催化机理,具体包含了Sn基均相催化剂材料(例如Sn基含氟双相体系催化剂),Sn基异相催化剂材料(例如Sn基沸石,Sn基介孔复合物,Sn基粘土,Sn基金属氧化物,以及Sn基聚合物催化剂).最后,对以H_2O_2为氧化剂的BV反应的Sn基催化剂的实际应用进行了评论和展望,讨论了它们在提高BV氧化反应催化活性方面可能的改进和发展的方向.
Baeyer-Villiger(BV) oxidation is one of the most important transformation reactions in synthetic organic chemistry. Catalytic versions of the BV oxidation are particularly attractive in practical applications, because the catalytic transformation substantially simplifies reaction process while minimizing reactant consumption as well as waste production. Further benefits are expected from replacing peracids, the traditionally used oxidant, by low cost and environmentally friendly hydrogen peroxide(H_2O_2). This review will first introduce very briefly the features of BV oxidation reactions, and the corresponding oxidants traditionally used. Afterwards, the emphasis will be placed on the specific Sn-based catalysts, their performance comparison for the BV oxidation reaction by using H_2O_2 as oxidant,and the catalytic mechanisms of most Sn-based catalysts reported so far, including homogeneous Sn-based catalysts(such as Sn-based fluorous biphase system catalysts), heterogeneous Sn-based catalysts(such as Sn-based zeolite catalysts, Sn-based mesoporous composites, Sn-incorporated clay catalysts, Sn-based metal oxide composites and polymer supported Sn catalysts). Finally, the Sn-based catalysts for BV oxidation are outlooked for their potentials and perspectives in enhancing the performance and then accelerating the practical applications of BV oxidations by using H_2O_2. The developing direction of the Sn-based catalytic BV reaction is also illustrated.
基金
supported by the National Key Basic Research Program of China(2013CB933200)
the National Natural Science Foundation of Shanghai(16ZR1440600)
