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Metal-Free Visible-Light-Induced Direct Synthesis of Alkyl-Substituted Phosphonodithioates from White Phosphorus (P4)
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2024-12-06 , DOI: 10.1002/adsc.202401355
Fengxiao Wang, Xiyuan Zhang, Jiaming Xu, Qitao Shen, Bo Jiang, Zhiwei Miao

The direct synthesis of organic phosphorus compounds from white phosphorus (P4) is a longstanding challenge in organic synthesis. Here, we present a novel visible light-induced three-component functionalization reaction that integrates P4, disulfide compounds, and N-hydroxyphthalimide (NHPI) esters to produce alkyl-substituted phosphonodithioates in a one-pot process. Using 2,4,5,6-tetrakis(carbazol-9-yl)-1,3-dicyanobenzene (4CzIPN) as a photocatalyst, blue LEDs (456 nm) as the light source, and N,N-diisopropylethylamine (DIPEA) as the reducing agent in an acetone-toluene solvent system, this method achieves moderate to good yields of structurally diverse phosphonodithioates. The reaction proceeds under mild conditions, ensures complete conversion of P4, avoids chlorination, and uses inexpensive, readily available starting materials, offering potential for large-scale applications.



中文翻译:


从白磷中无金属可见光诱导直接合成烷基取代的膦酰硫代酸酯 (P4)



从白磷 (P4) 直接合成有机磷化合物是有机合成中一个长期的挑战。在这里,我们提出了一种新型的可见光诱导的三组分官能团化反应,该反应将 P4、二硫化物化合物和 N-羟基邻苯二酰亚胺 (NHPI) 酯整合在一起,在一锅法工艺中生产烷基取代的膦酰硫代酸酯。使用2,4,5,6-四(咔唑-9-基)-1,3-二氰基苯(4CzIPN)作为光催化剂,蓝色LED(456 nm)作为光源,N,N-二异丙基乙胺(DIPEA)作为丙酮-甲苯溶剂系统中的还原剂,该方法实现了结构多样的膦酰硫酸盐的中等到良好产率。该反应在温和的条件下进行,确保 P4 的完全转化,避免氯化,并使用廉价、现成的起始材料,为大规模应用提供了潜力。

更新日期:2024-12-06
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