Department of Chemistry, National Tsing Hua University, Hsinchu, Taiwan, P.R. China.
ChemSusChem. 2020 Jan 19;13(2):287-292. doi: 10.1002/cssc.201901813. Epub 2019 Sep 30.
Herein the first visible-light-activated Sonogashira C-C coupling reaction at room temperature catalyzed by single-metal heterogeneous Cu O truncated nanocubes (Cu O TNCs) was developed. A wide variety of aryl halides and terminal alkynes worked well in this recyclable heterogeneous photochemical process to form the corresponding Sonogashira C-C coupling products in good yields. Mechanistic control studies indicated that CO enhances the formation of light-absorbing heterogeneous surface-bound Cu -phenylacetylide (λ =472 nm), which further undergoes single-electron transfer with aryl iodides/bromides to enable Sonogashira C -C bond formation. In contrast to literature-reported bimetallic TiO -containing nanoparticles as photocatalyst, this work avoided the need of cocatalysis by TiO . Single-metal Cu in Cu O TNCs was solely responsible for the observed C -C coupling reactions under CO atmosphere.
本文首次报道了在单金属异质 CuO 截断纳米立方体（CuO TNCs）室温可见光催化下的 Sonogashira C-C 偶联反应。该可回收的非均相光化学反应对各种芳基卤化物和末端炔烃具有良好的适用性，以高产率得到相应的 Sonogashira C-C 偶联产物。机理控制研究表明，CO 增强了吸光异质表面结合的 Cu-苯乙炔（λ=472nm）的形成，该物质进一步与芳基碘化物/溴化物进行单电子转移，从而实现 Sonogashira C-C 键的形成。与文献报道的含 TiO2 的双金属纳米颗粒作为光催化剂相比，本工作避免了 TiO2 共催化的需要。在 CO 气氛下，CuO TNCs 中的单金属 Cu 负责观察到的 C-C 偶联反应。
