Adduct-catalyzed tandem electro-thermal synthesis of organophosphorus(III)compounds from white phosphorus  

作　　者：Jingcheng Hu Haoyu He Minghao Xu Xiaotian Qi Chao Fu Hong Yi Aiwen Lei 胡精诚;何浩宇;徐铭昊;戚孝天;付超;易红;雷爱文

机构地区：[1]College of Chemistry and Molecular Sciences,The Institute for Advanced Studies(IAS),Wuhan University,Wuhan 430072,China [2]Department of Electrical Engineering,North China Electric Power University,Baoding 071003,China

出　　处：《National Science Review》2025年第3期201-210,共10页国家科学评论(英文版)

基　　金：supported by the National Key R&D Program of China(2021YFA1500100,A.L.);the National Natural Science Foundation of China(22031008,A.L.);the Science Foundation of Wuhan(2020010601012192,A.L.).

摘　　要：Electrooxidation strategies for synthesizing readily oxidizable products face notable challenges,especially when the oxidation potential of the products is lower than that of the reactants or when high current densities are necessary.The electrooxidation synthesis of trivalent organophosphorus compounds(OPCs(III))from white phosphorus(P_(4))has demonstrated potential but is hindered by selectivity issues due to over-oxidation.Herein,we report a tandem electro-thermal synthesis pathway that addresses these challenges in producing OPCs(III)from P_(4).The process begins with an electrooxidation step that generates a stable trivalent phosphorus transfer reagent,then thermochemically converted into various high-value OPCs(III).Utilizing hexafluoroisopropanol(HFIP)as the nucleophile and optimizing a tetrabutylammonium iodide(TBAI)-4-dimethylaminopyridine(DMAP)-adduct catalytic system,we developed an efficient electrophilic phosphorus transfer reagent via electrosynthesis.The adduct facilitates the oxidation of P_(4)and enhances the nucleophilicity of HFIP,thereby improving the electrooxidation process.This approach supports high current density,scales up to the hundred-gram level without yield loss,and remains compatible with fluctuating green electricity.

关 键 词：organic electrosynthesis P_(4)activation trivalent organophosphorus adduct-catalyzed green electricity 

分 类 号：O621.1[理学—有机化学]