State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing, 100191, China.
State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2019 Mar 26;58(14):4566-4570. doi: 10.1002/anie.201814570. Epub 2019 Feb 7.
Although the application of 1,2-dichloroethane (DCE) as a chlorinating reagent in organic synthesis with the concomitant release of vinyl chloride as a useful byproduct is a fantastic idea, it still presents a tremendous challenge and has not yet been achieved because of the harsh dehydrochlorination conditions and the sluggish C-H chlorination process. Here we report a bifunctional electrocatalysis strategy for the catalytic dehydrochlorination of DCE at the cathode simultaneously with anodic oxidative aromatic chlorination using the released HCl as the chloride source for the efficient synthesis of value-added (hetero)aryl chlorides. The mildness and practicality of the protocol was further demonstrated by the efficient late-stage chlorination of bioactive molecules.
虽然 1,2-二氯乙烷（DCE）作为一种氯化试剂在有机合成中的应用具有很大的吸引力，因为可以同时释放出氯乙烯作为有用的副产物，但由于苛刻的脱氯化氢条件和缓慢的 C-H 氯化反应过程，这仍然是一个巨大的挑战，尚未实现。在这里，我们报道了一种双功能电催化策略，用于在阴极同时催化 DCE 的脱氯化氢反应，以及使用释放的 HCl 作为氯化物源的阳极氧化芳香族氯化反应，以高效合成有价值的（杂）芳基氯化物。该方案的温和性和实用性通过生物活性分子的高效后期氯化进一步得到证明。
