Yuan Kang-Ning, Xie Tian, Wang Jia-Bao, Wang Dali, Shang Ming
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China.
School of Chemistry and Chemical Engineering, Zhangjiang Institute for Advanced Study, Shanghai Jiao Tong University, Shanghai, 200240, China.
Angew Chem Int Ed Engl. 2025 Apr 7;64(15):e202500744. doi: 10.1002/anie.202500744. Epub 2025 Feb 7.
A photoelectrocatalytic method is presented that achieves direct decarboxylative C(sp)-P coupling, providing a modular route to alkylphosphinates and alkylphosphonates from readily available carboxylic acids. The success of this reaction hinges on the synergistic combination of electrochemical anodic oxidation and photocatalytic ligand to metal charge transfer (LMCT) decarboxylation. By employing P(III) reagents as limiting reagents, our approach enables efficient alkyl modification of medicinally important nucleosides and complex molecules derived phosphonites, which were challenging to access by existing methods. Detailed mechanistic studies elucidate the critical roles of Fe catalysts and additives, offering valuable insights into the reaction pathway and laying the foundation for future advancements in photoelectrocatalytic C(sp)-heteroatom bond-forming reactions.
本文提出了一种光电催化方法，该方法可实现直接脱羧C(sp)-P偶联反应，为从易得的羧酸制备次膦酸烷基酯和膦酸烷基酯提供了一种模块化途径。该反应的成功取决于电化学阳极氧化和光催化配体到金属电荷转移（LMCT）脱羧反应的协同结合。通过使用P(III)试剂作为限量试剂，我们的方法能够对具有重要药用价值的核苷和衍生自亚磷酸酯的复杂分子进行有效的烷基修饰，而这些是现有方法难以实现的。详细的机理研究阐明了铁催化剂和添加剂的关键作用，为反应途径提供了有价值的见解，并为光电催化C(sp)-杂原子键形成反应的未来发展奠定了基础。
