题 目: Enhanced Photoinduced Baeyer−Villiger Oxidation of Ketones by Introducing Trinuclear Ruthenium Clusters into PolyoxometalateBased Metal−Organic Frameworks
作 者: Yanan Liu, Jing Wang, Luoning Li, Sha Meng, Kaihui Ji, Pengtao Ma, Jingping Wang,* and Jingyang Niu*
刊 名: Chem. Mater.
年卷页: 2023, 35, 3941-3950.
摘 要：The development of solar-driven organic synthesis processes as an alternative to conventional thermo-catalytic technologies is of great research significance in academia and industry. Herein, we looked into the photoinduced Baeyer−Villiger oxidation of cyclohexanone based on the Mukaiyama method for the first time. We fabricated a crystalline polyoxometalate-based metal−organic framework photocatalyst, CR-SiW12, which represents the first example of trinuclear ruthenium clusters involved in the construction of polyoxometalate-based metal−organic frameworks. The cyclohexanone was efficiently converted to ε-caprolactone under visible light (>400 nm) irradiation with CR-SiW12 as the catalyst, with a reaction turnover number and turnover frequency recorded as 941 and 274.5 h−1 , respectively, and the apparent quantum yield at 465 nm was measured to be 8.4%. Moreover, CR-SiW12 exhibited high structural stability and reaction reusability where reaction yield remained high at 91.3% after five consecutive reaction cycles. This work offers a promising strategy for accomplishing Baeyer−Villiger oxidation reactions under green conditions.
文章链接：https://doi.org/10.1021/acs.chemmater.3c00120
