Modular and Mild Assembly of Aryl Phosphines, Phosphine Oxides/Sulfides, Phosphinates, and Phosphonates Enabled by Photoinduced Divergent Construction of Aryl-P(III) and Aryl-P(V) Bonds

作者：Hanhan Sun, Dan Wu, Fengying Yan, Yuhuan Han, Jingru Leng, Shuo Jin, Ping Zhang, Zhenhua Gu, Xianwei Sui · 发表于：JACS Au · 年份：2026 · DOI：10.1021/jacsau.6c00021 · 被引用次数：1 · 研究领域：Radical Photochemical Reactions、Catalytic Cross-Coupling Reactions、Sulfur-Based Synthesis Techniques

Phosphines and their derivatives feature prominently in organic synthesis, medicinal chemistry, and material science. Yet, a general synthetic platform for the modular and mild assembly of these compounds remains elusive. Herein, a metal-free photoinduced divergent formation of aryl-P-(III) and aryl-P-(V) has been established employing dibenzothiophenium salts as the aryl radical precursor and structurally amendable oxylphosphines as the partners by tuning the thermodynamic and kinetic parameters. A variety of structurally diverse triaryl phosphines, phosphine oxides/sulfides, and phosphinates, as well as phosphonates, were modularly assembled under mild conditions from easily available oxylphosphine and arenes. This photoinduced version provides a mild and versatile protocol complementary to the Michaelis-Arbuzov reaction. Notably, this photoinduced methodology was compatible with halide functionalities (Cl, Br, OTf), and the combination of this method with classic two-electron approaches showed great value in the synthesis of unsymmetrical phosphine ligands. Preliminary mechanistic studies for this methodology were also investigated.