Department of Chemistry, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea.
Center for Catalytic Hydrocarbon Functionalizations, Institute for Basic Science (IBS), Daejeon 34141, Republic of Korea.
Science. 2020 Oct 9;370(6513):214-219. doi: 10.1126/science.abb6375.
In place of functional groups that impose different inductive effects, we immobilize molecules carrying thiol groups on a gold electrode. By applying different voltages, the properties of the immobilized molecules can be tuned. The base-catalyzed saponification of benzoic esters is fully inhibited by applying a mildly negative voltage of -0.25 volt versus open circuit potential. Furthermore, the rate of a Suzuki-Miyaura cross-coupling reaction can be changed by applying a voltage when the arylhalide substrate is immobilized on a gold electrode. Finally, a two-step carboxylic acid amidation is shown to benefit from a switch in applied voltage between addition of a carbodiimide coupling reagent and introduction of the amine.
我们将携带巯基的分子固定在金电极上，取代具有不同诱导效应的官能团。通过施加不同的电压，可以调节固定分子的性质。通过施加相对于开路电位为-0.25 伏的轻微负电压，可以完全抑制苯甲酸酯的碱催化皂化。此外，当芳基卤化物底物固定在金电极上时，施加电压可以改变 Suzuki-Miyaura 交叉偶联反应的速率。最后，通过在添加碳二亚胺偶联试剂和引入胺之间切换施加的电压，显示出两步羧酸酰胺化反应从中受益。
