Department of Chemistry , Shiraz University , Shiraz 7194684795 , I. R. Iran.
J Org Chem. 2019 Nov 1;84(21):13503-13515. doi: 10.1021/acs.joc.9b01759. Epub 2019 Sep 26.
Photoredox catalysis in recent years has manifested a powerful branch of science in organic synthesis. Although merging photoredox and metal catalysts has been a widely used method, switchable heterogeneous photoredox catalysis has rarely been considered. Herein, we open a new window to use a switchable heterogeneous photoredox catalyst which could be turned on/off by changing a simple stimulus (O) for two opponent reactions, namely, oxidative and protodecarboxylation. Using this strategy, we demonstrate that Au@ZnO core-shell nanoparticles could be used as a switchable photocatalyst which has good catalytic activity to absorb visible light due to the localized surface plasmon resonance effect of gold, can decarboxylate a wide range of aromatic and aliphatic carboxylic acids, have multiple reusability, and are a reasonable candidate for synthesizing both aldehydes/ketones and alkane/arenes in a large-scale set up. Some biologically active molecules are also shown via examples of the direct oxidative and protodecarboxylation which widely provided pharmaceutical agents.
近年来，光氧化还原催化在有机合成中表现出强大的科学分支。尽管将光氧化还原和金属催化剂结合使用是一种广泛应用的方法，但可切换的多相光氧化还原催化很少被考虑。在此，我们开辟了一个新的窗口，使用一种可切换的多相光氧化还原催化剂，通过改变一个简单的刺激（O）可以为两个相反的反应（即氧化和脱羧）打开/关闭。利用这一策略，我们证明了 Au@ZnO 核壳纳米粒子可以作为一种光催化剂，由于金的局域表面等离子体共振效应，它具有良好的可见光吸收催化活性，可以脱羧化广泛的芳香族和脂肪族羧酸，具有多次可重复使用性，并且是在大规模设置中合成醛/酮和烷/芳烃的合理候选物。一些生物活性分子也通过直接氧化和脱羧的例子得到了广泛的药物制剂。
