College of Pharmacy, Third Military of Medical University, Chongqing 400038, PR China.
College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, Sichuan 643000, PR China.
J Org Chem. 2022 Apr 1;87(7):4742-4749. doi: 10.1021/acs.joc.2c00031. Epub 2022 Mar 18.
The synthesis of porphyrin and chlorin derivatives has attracted significant attention due to their numerous applications. Herein, we report an environment friendly oxidant- and catalyst-free electrooxidative cross-coupling approach for multiple coupling reactions to synthesize C-N, C-O, and C-S substituted porphyrin and chlorin derivatives. For C-N cross-coupling reactions, diaminated porphyrins were obtained as the main products, while using 4-bromo-2,6-dimethyl aniline resulted in monoaminated product. Similarly, electrochemical catalysis of porphyrins with phenol and thiophene produced -disubstituted porphyrins in moderate yields under a smaller current. Chlorins were also applicable, and 20-substituted products were efficiently produced regioselectively. To the best of our knowledge, this work represents the first example of electrooxidative C-X cross-coupling of porphyrins and chlorins.
由于其众多的应用，卟啉和氯卟啉衍生物的合成引起了人们的极大关注。在此，我们报道了一种环境友好的氧化剂和催化剂免费的电化学交叉偶联方法，用于多种偶联反应，以合成 C-N、C-O 和 C-S 取代的卟啉和氯卟啉衍生物。对于 C-N 交叉偶联反应，主要得到二氨基化卟啉作为产物，而使用 4-溴-2,6-二甲基苯胺则得到单氨基化产物。同样，在较小电流下，电化学催化卟啉与苯酚和噻吩反应，以中等产率生成 -二取代卟啉。氯卟啉也适用，并且可以有效地选择性区域生成 20-取代产物。据我们所知，这项工作代表了卟啉和氯卟啉的电氧化 C-X 交叉偶联的首例。
