Recent Advances of the Atherton-Todd Reaction

doi:10.6023/cjoc202210032

Abstract

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

Cite this article

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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Fig. & Tab. 32

Scheme 1. Representative active compounds containing phosphoramide or phosphate moiety

Scheme 2. Classical Atherton-Todd reaction

Scheme 3. Origin of the Atherton-Todd reaction

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

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

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

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

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

Scheme 9. Sodium hydroxide-mediated Atherton-Todd reaction

Scheme 10. I2-catalyzed Atherton-Todd reaction

Scheme 11. Selectfluor-mediated Atherton-Todd reaction

Scheme 12. Trichloroisocyanuric acid-mediated Atherton-Todd reaction

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

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

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

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

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

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

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

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

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

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

Scheme 23. Other Atherton-Todd-type reaction

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

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

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

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

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

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

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

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

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

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Atherton-Todd反应的研究进展