Dong Yueyue, Su Yanling, Du Lili, Wang Ruifeng, Zhang Li, Zhao Dongbing, Xie Wei
Key Lab of Advanced Energy Materials Chemistry (Ministry of Education), Renewable Energy Conversion and Storage Center, College of Chemistry , Nankai University , Weijin Road 94 , Tianjin 300071 , China.
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry , Nankai University , Weijin Road 94 , Tianjin 300071 , China.
ACS Nano. 2019 Sep 24;13(9):10754-10760. doi: 10.1021/acsnano.9b05523. Epub 2019 Sep 9.
Deuteration has found important applications in synthetic chemistry especially for pharmaceutical developments. However, conventional deuteration methods using transition-metal catalysts or strong bases generally involve harsh reaction conditions, expensive deuterium source, insufficient efficiency, and poor selectivity. Herein, we report an efficient visible-light-driven dehalogenative deuteration of organic halides using plasmonic Au/CdS as photocatalyst and DO as deuterium donor. Electron transfer from Au to CdS, which has been confirmed by surface-enhanced Raman spectroscopy, plays a decisive role for the plasmon-mediated dehalogenation. The deuteration is revealed to proceed a radical pathway in which substrates are first activated by the photoinduced electron transfer to generate aryl radicals, and the radicals are further trapped by DO to give deuterated products. Under visible-light irradiation, excellent deuteration efficiency is achieved with high functional group tolerance and a wide range of substrates at room temperature. Compared with bare CdS, the photocatalytic activity increases ∼18 times after the loading of plasmonic Au nanoparticles. This work sheds light on the interfacial charge transfer between plasmonic metals and semiconductors as an important criterion for rational design of visible-light photocatalysts.
氘代在合成化学中已发现重要应用，尤其在药物研发方面。然而，使用过渡金属催化剂或强碱的传统氘代方法通常涉及苛刻的反应条件、昂贵的氘源、效率不足以及选择性差等问题。在此，我们报道了一种使用等离子体Au/CdS作为光催化剂和DO作为氘供体的有机卤化物的高效可见光驱动脱卤氘代反应。表面增强拉曼光谱已证实从Au到CdS的电子转移，其在等离子体介导的脱卤反应中起决定性作用。该氘代反应显示通过自由基途径进行，其中底物首先通过光诱导电子转移被活化以生成芳基自由基，然后这些自由基被DO捕获以得到氘代产物。在可见光照射下，在室温下实现了具有高官能团耐受性和广泛底物范围的优异氘代效率。与裸CdS相比，负载等离子体Au纳米颗粒后光催化活性提高了约18倍。这项工作揭示了等离子体金属与半导体之间的界面电荷转移，作为合理设计可见光光催化剂的重要标准。
