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DOI: https://doi.org/10.6023/cjoc202608013

研究论文

以六氟化硫为氟源的电化学氧化氟化膦氧化物

  • 赵跃 ,
  • 朱姗 ,
  • 马凤翔 ,
  • 林涛 ,
  • 杭忱 ,
  • 曹骏 ,
  • 宋玉梅
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  • a国网安徽省电力有限公司电力科学研究院, 合肥, 230601

收稿日期: 2026-08-12

  修回日期: 2026-09-09

  网络出版日期: 2026-09-22

基金资助

国网安徽省电力有限公司科技项目(B3120524000K)资助.

收起

Electrochemical Oxidative Fluorination of Phosphine Oxides with Sulfur Hexafluoride

  • Yue Zhao ,
  • Shan Zhu ,
  • Fengxiang Ma ,
  • Tao Lin ,
  • Chen Hang ,
  • Jun Cao ,
  • Yumei Song
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  • aState Grid Anhui Electric Power Research Institute, Hefei, 230601

Received date: 2026-08-12

  Revised date: 2026-09-09

  Online published: 2026-09-22

Supported by

State Grid Anhui Electric Power Co., Ltd. Technology Project (No. B3120524000K).

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摘要

有机磷氟化物是化学生物学、药物化学和合成中的重要结构单元,然而其制备通常依赖于昂贵或操作要求苛刻的氟化试剂。本文报道了一种以六氟化硫（SF6）为氟源、对膦氧化物进行恒流电化学氧化氟化的方法。该反应在室温下进行,采用碳棒阳极和锡阴极,以四丁基醋酸铵和DBU在1,2-二氯乙烷/乙腈混合溶剂中反应。一系列二芳基和烷基取代的膦氧化物被转化为相应的P(O)-F产物,分离产率中等至良好,最高可达72%。该转化被认为将SF6的阴极单电子还原与膦氧化物的阳极氧化相结合。氟负离子捕获生成的膦酰基自由基阳离子,随后经质子耦合电子转移,形成P(O)-F键。本研究为利用一种持久性含氟温室气体作为有机磷合成的氟原料提供了一条电极驱动的途径.

关键词： 六氟化硫; 电化学; 氧化氟化; 膦氧化物; 膦氟键

本文引用格式

赵跃 , 朱姗 , 马凤翔 , 林涛 , 杭忱 , 曹骏 , 宋玉梅 . 以六氟化硫为氟源的电化学氧化氟化膦氧化物[J]. 有机化学, 0 : 202608013 . DOI: 10.6023/cjoc202608013

Abstract

Organophosphorus fluorides are valuable motifs in chemical biology, medicinal chemistry, and synthesis, yet their preparation commonly relies on costly or operationally demanding fluorinating reagents. Herein, we describe a constant-current electrochemical oxidative fluorination of phosphine oxides using sulfur hexafluoride (SF6) as the fluorine source. A range of diaryl and alkyl-substituted phosphine oxides is converted to the corresponding P(O)-F products in moderate to good isolated yields, reaching up to 72%. The transformation is proposed to combine cathodic single-electron reduction of SF6, which furnishes fluoride-containing reduced fragments, with anodic oxidation of the phosphine oxide. Fluoride capture of the resulting phosphinoyl radical cation, followed by proton-coupled electron transfer, furnishes the P(O)-F bond. This study provides an electrode-driven route to use a persistent fluorinated greenhouse gas as a fluorine feedstock for organophosphorus synthesis.

Key words： sulfur hexafluoride; electrochemistry; oxidative fluorination; phosphine oxides; phosphorus-fluorine bond

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