Achieving highly regioselective synthesis in organic chemistry is challenging due to the uncontrollable orientation between reacting partners. External electric fields (EEFs) can influence the reactivity and selectivity of the substrate by causing directional adsorption. However, scalable and efficient techniques for using EEFs as “smart catalysts” have been lacking, hindering their application. In this study, we present a novel method for modifying the regioselectivity of quinoxaline-2(1H)-ones by functionalizing their C7-position using the electric double layer (EDL) theory. This approach led to moderate to good yields of the corresponding C7-thiocyanation products. DFT calculations and control experiments demonstrated that EEFs could reverse the regioselectivity of quinoxaline-2(1H)-ones, allowing the C7-thiocyanation to proceed via a radical reaction mechanism. Additionally, the resulting 7-thiocyano-1-methylquinoxaline-2(1H)-ones exhibited promising AIE properties. Our work showcases a promising strategy for achieving highly regioselective functionalization by aligning the electric field with the desired reaction/bond axis.

由于反应伙伴之间的方向无法控制，在有机化学中实现高度区域选择性合成具有挑战性。外部电场 (EEF) 可以通过引起定向吸附来影响底物的反应性和选择性。然而，使用 EEF 作为“智能催化剂”的可扩展且高效的技术一直缺乏，阻碍了其应用。在这项研究中，我们提出了一种利用双电层（EDL）理论对喹喔啉-2(1 H )-酮的C7位进行功能化来改变其区域选择性的新方法。这种方法产生了相应的 C7-硫氰化产物的中等至良好的产率。 DFT计算和对照实验表明，EEF可以逆转喹喔啉-2(1 H )-酮的区域选择性，从而允许C7-硫氰化通过自由基反应机制进行。此外，所得的 7-硫氰基-1-甲基喹喔啉-2(1 H )-酮表现出有前景的 AIE 特性。我们的工作展示了一种有前途的策略，通过将电场与所需的反应/键合轴对齐来实现高度区域选择性功能化。