Department of Chemistry, Tianjin Key Laboratory of Molecular Optoelectronic Sciences, and, Tianjin Collaborative Innovation Centre of Chemical Science & Engineering, Tianjin University, Tianjin, 300072, P. R. China.
Joint School of NUS & TJU, International Campus of Tianjin University, Fuzhou, 350207, P. R. China.
Chemistry. 2020 Apr 24;26(24):5515-5521. doi: 10.1002/chem.202000517. Epub 2020 Apr 15.
Herein we report a novel and straightforward protocol for the construction of valuable gem-BPs by means of proton-coupled electron-transfer (PCET)-triggered enamido C(sp )-H diphosphorylation. This reaction represents a rare example of realizing the challenging double C-P bond formation at a single carbon atom, thus providing facile access to a broad variety of structurally diverse bisphosphonates from simple enamides under silver-mediated conditions. Initial mechanistic studies demonstrated that the diphosphorylation involves two rounds of PCET-initiated radical relay process.
在此,我们报告了一种新颖而直接的方法,通过质子耦合电子转移(PCET)引发的烯酰胺 C(sp )-H 双膦酰化反应来构建有价值的宝石-BPs。该反应代表了在单个碳原子上实现具有挑战性的双 C-P 键形成的罕见实例,因此在银介导条件下,从简单的烯酰胺中可轻松获得广泛的结构多样的双膦酸酯。初步的机理研究表明,双膦酰化反应涉及两轮 PCET 引发的自由基接力过程。