Atherton-Todd反应的研究进展

doi:10.6023/cjoc202210032

摘要/Abstract

磷酰胺或磷酸酯类化合物及其衍生物是一类非常重要的含磷有机分子, 在药物化学、材料化学以及有机催化等研究领域均有着广泛应用. Atherton-Todd反应是制备这类化合物最有效的方法之一, 该反应是指氧磷氢化合物[P(O)- H]在碱的作用下与四氯化碳原位生成磷酰氯[P(O)-Cl]中间体, 随后该中间体与醇或胺类化合物反应形成相应的磷酸酯或磷酰胺类化合物及其衍生物. 近年来, Atherton-Todd反应由于其操作容易、原子经济性高、底物普适性广以及易于将含磷原子引入到活性化合物结构片段中等优点, 受到了合成化学家的广泛关注. 总结近几十年来Atherton-Todd反应的研究进展及其在有机合成中的应用, 并对目前该领域可能存在的研究挑战提出展望, 希望能为Atherton-Todd反应的未来发展方向提供一些借鉴和思考.

关键词: 有机磷化合物, Atherton-Todd反应, 活性中间体, 不对称催化

Phosphoramides or phosphates and their derivatives are a very important class of phosphorus-containing organic molecules, which are widely applied in medicinal chemistry, material chemistry and organic catalysis. As one of the most effective methods towards constructing phosphorus compounds, the Atherton-Todd reaction involves in situ halogenation of P(O)-H molecules with tetrachloromethane to generate the key intermediates of phosphoryl chlorides in the presence of bases, which subsequently react with amines or alcohols to form the corresponding phosphoramide or phosphate products. In recent years, this reaction has been widely explored by synthetic chemists due to its ease of operation, high atom economy, broad substrate versatility, and ease of incorporation of phosphorus units into active structural fragments. The research progress of the Atherton-Todd reaction and its application in organic synthesis in recent decades are summarized, and a brief outlook on the current research challenges is put forward, hoping to provide reference and thinking for the further development of the Atherton-Todd reaction.

Key words: organophosphorus compounds, Atherton-Todd reaction, active intermediates, asymmetric catalysis

引用此文

方思强, 刘赞娇, 王天利. Atherton-Todd反应的研究进展[J]. 有机化学, 2023, 43(3): 1069-1083.

Siqiang Fang, Zanjiao Liu, Tianli Wang. Recent Advances of the Atherton-Todd Reaction[J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1069-1083.

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图/表 32

图式1. 代表性的含磷酰胺或磷酸酯结构片段的活性化合物

Scheme 1. Representative active compounds containing phosphoramide or phosphate moiety

图式2. 经典的Atherton-Todd反应

Scheme 2. Classical Atherton-Todd reaction

图式3. Atherton-Todd反应的起源

Scheme 3. Origin of the Atherton-Todd reaction

图式4. Atherton-Todd反应中主要的磷活性中间体

Scheme 4. Key active phosphorus intermediates in the Atherton- Todd reaction

图式5. Atherton-Todd反应中磷活性物种的分离

Scheme 5. Isolation of active phosphorus species in the Atherton-Todd reaction

图式6. Atherton-Todd反应中三氯甲基负离子中间体研究

Scheme 6. Research on the trichloromethyl anion intermediate in the Atherton-Todd reaction

图式7. Roundhill小组提出的亚磷酸甲酯的Atherton-Todd反应机理

Scheme 7. Mechanism of the Atherton-Todd reaction of methyl phosphinate proposed by Roundhill group

图式8. 五配位稠双环膦氢化合物的Atherton-Todd反应机理

Scheme 8. Mechanism of the Atherton-Todd reaction of penta- coordinated fused bicyclic phosphorane compounds

图式9. 次氯酸钠介导的Atherton-Todd反应

Scheme 9. Sodium hydroxide-mediated Atherton-Todd reaction

图式10. 碘催化的Atherton-Todd反应

Scheme 10. I2-catalyzed Atherton-Todd reaction

图式11. Selectfluor介导的Atherton-Todd反应

Scheme 11. Selectfluor-mediated Atherton-Todd reaction

图式12. 三氯代异氰尿酸介导的Atherton-Todd反应

Scheme 12. Trichloroisocyanuric acid-mediated Atherton-Todd reaction

图式13. 电催化的氧磷氢化合物和胺类化合物的交叉偶联反应

Scheme 13. Electrocatalytic cross-coupling of P(O)H compounds with amines

图式14. 电催化的氧磷氢化合物和硫醇类化合物的交叉偶联反应

Scheme 14. Electrocatalytic cross-coupling of P(O)H compounds with thiols

图式15. Cu(OAc)2催化的Atherton-Todd-type反应

Scheme 15. Cu(OAc)2-catalyzed Atherton-Todd-type reaction

图式16. CuI催化的Atherton-Todd-type反应

Scheme 16. CuI-catalyzed Atherton-Todd-type reaction

图式17. Fe(AcAc)2催化的Atherton-Todd-type反应

Scheme 17. Fe(AcAc)2-catalyzed Atherton-Todd-type reaction

图式18. Pd2dba3催化的Atherton-Todd-type反应

Scheme 18. Pd2dba3-catalyzed Atherton-Todd-type reaction

图式19. Ni(OAc)2/Y(OTf)3催化的Atherton-Todd-type反应

Scheme 19. Ni(OAc)2/Y(OTf)3-catalyzed Atherton-Todd-type reaction

图式20. 亚甲蓝作为光敏剂促进的光催化Atherton-Todd型反应

Scheme 20. Electrocatalytic Atherton-Todd-type reaction promoted by methylene blue as photosensitizer

图式21. 光催化的Atherton-Todd-type反应

Scheme 21. Light-catalyzed Atherton-Todd-type reaction

图式22. Cs2CO3促进的Atherton-Todd-type反应

Scheme 22. Cs2CO3-promoted Atherton-Todd-type reaction

图式23. 其他的Atherton-Todd-type反应

Scheme 23. Other Atherton-Todd-type reaction

图式24. Aaron小组对Atherton-Todd反应立体化学的研究

Scheme 24. Stereochemistry of the Atherton-Todd reaction by Aaron’s group

图式25. Han小组对Atherton-Todd反应立体化学的研究

Scheme 25. Stereochemistry of the Atherton-Todd reaction by Han’s group

图式26. 手性五配位膦氢化合物的Atherton-Todd反应的立体化学研究

Scheme 26. Stereochemistry of the Atherton-Todd reaction of chiral pentacoordinate hydrophosphoranes

图式27. 空间位阻对Atherton-Todd反应立体化学的影响

Scheme 27. Effect of steric hindrance on the stereochemistry of the Atherton-Todd reaction

图式28. Atherton-Todd反应在芳基酚脱氧反应中的应用

Scheme 28. Application of the Atherton-Todd reaction in deoxygenation of arylphenol compounds

图式29. Atherton-Todd反应在功能小分子合成中的应用

Scheme 29. Application of the Atherton-Todd reaction in the synthesis of functional small molecules

图式30. 手性亚砜介导外消旋氧磷氢化合物的动态动力学拆分

Scheme 30. Chiral sulfoxide-mediated dynamic kinetic resolution of racemic P(O)-H compounds

图式31. 二肽-季鏻盐催化的轴手性二酚及氨基酚的立体发散型动力学拆分

Scheme 31. Dipeptide-phosphonium salt-catalyzed enantiodivergent kinetic resolution of axial chiral diols and amino alcohols

图式32. 手性季鏻盐催化的亚砜亚胺化合物的去对称化反应

Scheme 32. Chiral quaternary phosphonium salt-catalyzed desymmetrization of sulfoximines

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