Single‐Atom Iron Catalyst as an Advanced Redox Mediator for Anodic Oxidation of Organic Electrosynthesis

• Published in: Angewandte Chemie International Edition Vol. 63; no. 27; pp. e202404295 - n/a
• Main Authors: Wang, Xin‐Yu, Pan, Yong‐Zhou, Yang, Jiarui, Li, Wen‐Hao, Gan, Tao, Pan, Ying‐Ming, Tang, Hai‐Tao, Wang, Dingsheng
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 01.07.2024; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Amides; Anodizing; Catalysts; Catalytic activity; Chemistry; Chemistry, Multidisciplinary; Electrocatalysts; Electrochemistry; Electron transfer; Indirect oxidation; Iron; Organic compounds; Organic electrosynthesis; Oxidation; Physical Sciences; Pyrolysis; Redox mediator; Science & Technology; Single-atom catalysts; Single-electron transfer; Substrates; FUNCTIONALIZATION; SITE; Single-atom catalysts; PLATINUM; Redox mediator; Organic electrosynthesis; Indirect oxidation; Single-electron transfer; WATER
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202404295

Homogeneous electrocatalysts can indirect oxidate the high overpotential substrates through single‐electron transfer on the electrode surface, enabling efficient operation of organic electrosynthesis catalytic cycles. However, the problems of this chemistry still exist such as high dosage, difficult recovery, and low catalytic efficiency. Single‐atom catalysts (SACs) exhibit high atom utilization and excellent catalytic activity, hold great promise in addressing the limitations of homogeneous catalysts. In view of this, we have employed Fe‐SA@NC as an advanced redox mediator to try to change this situation. Fe‐SA@NC was synthesized using an encapsulation‐pyrolysis method, and it demonstrated remarkable performance as a redox mediator in a range of reported organic electrosynthesis reactions, and enabling the construction of various C−C/C−X bonds. Moreover, Fe‐SA@NC demonstrated a great potential in exploring new synthetic method for organic electrosynthesis. We employed it to develop a new electro‐oxidative ring‐opening transformation of cyclopropyl amides. In this new reaction system, Fe‐SA@NC showed good tolerance to drug molecules with complex structures, as well as enabling flow electrochemical syntheses and gram‐scale transformations. This work highlights the great potential of SACs in organic electrosynthesis, thereby opening a new avenue in synthetic chemistry. We synthesized a single‐atom iron catalyst (Fe‐SA@NC), which exhibits good conversion efficiency in organic electro oxidation as an advanced redox mediator. This study provides valuable insights into the design of catalytic systems for organic tandem reactions from an inorganic chemistry aspect.