95 / 2023-09-28 11:48:29
Synthesis of Arylphosphonates via Ligand-Free Palladium-Catalyzed Michaelis-Arbuzov Reaction
Pd-catalysis; Triaryl phosphites; Aryl phosphonates; Michaelis-Arbuzov Reaction
摘要录用
张 进 / 海南大学
Chunya Li / Hainan University
皮 天树 / 女
Wei Hu / hainan university
Changxu Ye / 海南大学
Arylphosphonates are an important class of organophosphorus compounds widely used in medicinal chemistry and material sciences. For example, RU 468 can act as a glucocorticoid receptor antagonist, 1 is widely employed as a progesterone receptor antagonist[1][2]. Moreover, aromatic phosphonate compounds have excellent flame retardant properties, such as EHDPP, CDP and TPHP[3][4]. Importantly, mild and efficient synthesis protocol of these compounds are still limited. Currently, the synthesis of Aryl phosphonate compounds are mainly achieved by Friedel-Crafts arylation reaction[5] or Michaelis-Arbusov reaction[6]. However, the disadvantages of these methods such as use of toxic reagents (PCl3 etc.), heavy pollution, metered chemical additives((EtO)3P etc.) and harsh reaction conditions (160-320 oC.) are equally notable. Previously, our research group developed the isomerization of triaryl phosphites via the Michaelis-Arbusov rearrangement, but the required reaction temperature is still high(120-160 oC)[7].


During the investigation on the Michaelis-Arbusov Reaction, we found that the ligand-free Pd-catalyzed the reaction of aryl iodides with triaryl phosphites to generate the corresponding arylphosphates. Various substituted aryl iodides can only need to react with the equivalent triaryl phosphites at the reaction temperature of 60 oC for 2 h, that is, the corresponding arylphosphonates can be prepared at a good to high yields. The reaction process is green and has high conversion rate, which is the preparation method of aryl phosphates with certain industrial potential. Moreover, under similar conditions, the alkenyl iodides with the phosphites can also generate the corresponding aryl phosphates in very high yields, showing good substrate applicability.
重要日期
  • 会议日期

    11月12日

    2023

    11月16日

    2023

  • 10月24日 2023

    初稿截稿日期

  • 11月16日 2023

    注册截止日期

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