Wang Jinghao, Li Siyang, Yang Caoyu, Gao Huiwen, Zuo Lulu, Guo Zhiyu, Yang Pengqi, Jiang Yuheng, Li Jian, Wu Li-Zhu, Tang Zhiyong
CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology, Beijing, PR China.
University of Chinese Academy of Sciences, Beijing, PR China.
Nat Commun. 2024 Aug 12;15(1):6907. doi: 10.1038/s41467-024-51333-6.
Photoelectrochemical (PEC) cell is an ideal platform for organic transformation because of its green benefits and minimal energy consumption. As an emerging methodology, the reaction types of photoelectrocatalytic organic synthesis (PECOS) are limited to simple oxidation and C-H activation at current stage. Metal catalysis for the construction of C(sp)-N bonds has not been touched yet in PECOS. We introduce here a PEC method that successfully engages Ni catalysis for the mild production of aniline derivatives. Experimental and computational investigations elucidate that the addition of photoanode-generated amine radical to Ni catalyst avoids the sluggish nucleophilic attack, enabling the reaction to proceed at an ultra-low potential (-0.4 V vs. Ag/AgNO) and preventing the overoxidation of products in conventional electrochemical synthesis. This synergistic catalysis strategy exhibits good functional group tolerance and wide substrate scope on both aryl halides and amines, by which some important natural products and pharmaceutical chemicals have been successfully modified.
光电化学（PEC）电池因其绿色环保和低能耗的优点，是有机转化的理想平台。作为一种新兴方法，目前光电催化有机合成（PECOS）的反应类型仅限于简单氧化和C-H活化。在PECOS中，尚未涉及用于构建C(sp)-N键的金属催化。在此，我们介绍一种PEC方法，该方法成功地利用镍催化温和地制备苯胺衍生物。实验和计算研究表明，光阳极产生的胺自由基添加到镍催化剂上可避免缓慢的亲核攻击，使反应能够在超低电位（相对于Ag/AgNO为-0.4 V）下进行，并防止传统电化学合成中产物的过氧化。这种协同催化策略对芳基卤化物和胺类均表现出良好的官能团耐受性和广泛的底物范围，通过该策略已成功修饰了一些重要的天然产物和药物化学品。
