Recent Advances in the Synthesis of P-Stereogenic Compounds via Desymmetrization Strategy

doi:10.6023/cjoc202406029

Abstract

Organophosphorus compounds are extensively utilized in the field of medicine, materials, life sciences, and organic synthesis, among which chiral phosphorus compounds are the most widely used. Therefore, the construction of chiral phosphorus centers has always been the hotspot and challenge in organic synthesis. Traditional synthesis methods are mainly focused on chiral resolution and chiral induction strategies. Recently, the construction of chiral phosphorus centers via asymmetric catalysis has been well developed. The recently development of desymmetrization strategies in the construction of phos- phorus centers is summarized, mainly focused on the transformation of C—H, C=C, C≡C bonds and hydroxyl group. What’s more, the deficiencies of current strategies and the trends of future development have also been discussed.

Key words: P-stereogenic center, desymmetrization, C—H bond activation

Cite this article

Guotao Lin, Jian Xu, Qiuling Song. Recent Advances in the Synthesis of P-Stereogenic Compounds via Desymmetrization Strategy[J]. Chinese Journal of Organic Chemistry, 2024, 44(12): 3621-3638.

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Fig. & Tab. 38

Figure 1. Biologically molecules containing a P-stereogenic center

Scheme 1. Asymmetric deprotonation of dimethylphosphine

Scheme 2. Pd(II)-catalyzed synthesis of P?stereogenic phosphinamides via desymmetric C—H arylation

Scheme 3. Pd-catalyzed desymmetrization of intramolecular C—H bond activation in ortho-position of aryl

Scheme 4. Mechanism of Pd-catalyzed intramolecular C—H arylation

Scheme 5. Pd-catalyzed asymmetric C—H bond activation for the synthesis of P-stereogenic dibenzophospholes

Scheme 6. Synthesis of P-stereogenic phosphinamides via Pd(II)-catalyzed C—H alkynylation

Scheme 7. Pd(II)-catalyzed C(sp3)—H arylation toward P-ste- reogenic dialkylphosphinamides

Scheme 8. Rhodium(III)-catalyzed enantiotopic C—H activation enables access to P-chiral cyclic phosphinamides

Scheme 9. Iridium(III)-catalyzed C—H amidation of aryl- phosphoryls leading to a P-stereogenic center

Scheme 10. Ir-catalyzed enantioselective C—H amidations of phosphine oxides

Scheme 11. Ir-catalyzed C—H arylations enables access to P-chiral biaryl phosphine oxides

Scheme 12. Ir-catalyzed C—H coupling of tertiary substituted phosphine oxides with diarylacetylenes

Scheme 13. Iridium-catalyzed enantioselective C—H borylation of phosphinamides at m-position

Scheme 14. Iridium-catalyzed enantioselective C—H borylation of diarylphosphinates

Scheme 15. Cobalt-catalyzed enantioselective C—H functionalization of arylphosphinamides

Scheme 16. Cobalt-catalyzed enantioselective C—H alkoxylation and amination

Scheme 17. Electrochemical cobalt-catalyzed enantioselective C—H alkoxylation

Scheme 18. Electrochemical cobalt-catalyzed enantioselective C—H functionalization of arylphosphinamides

Scheme 19. Electrochemical cobalt-catalyzed enantioselective C—H esterification

Scheme 20. Lipase-catalyzed desymmetrization of a prochiral phosphine-borane

Scheme 21. Carbene-catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

Scheme 22. Biscinchona alkaloid catalyzd desymmetrization of bisphenols bearing a P-stereogenic center

Scheme 23. Pyridine-N-oxide catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

Scheme 24. Electrophilic selenium-catalyzed desymmetrizing cyclization reaction

Scheme 25. Rh-catalyzed desymmetrization of dialkynylphos- phine oxides

Scheme 26. Copper-catalyzed desymmetrization of diynes bear- ing a P-stereogenic center

Scheme 27. Thulium(III)-catalyzed desymmetrization of dialkynylphosphine oxides

Scheme 28. Gold-catalyzed desymmetrization of bisphenols bearing a P-stereogenic center

Scheme 29. Molybdenum-catalyzed asymmetric ring-closing metathesis

Scheme 30. Rhodium-catalyzed asymmetric arylation of phospholene oxides

Scheme 31. Rhodium-catalyzed desymmetrization of divinyl- phosphine oxides

Scheme 32. Hydrogen-bond-donor catalysis desymmetrization of phosphonic dichlorides

Scheme 33. Catalytic desymmetrization of phosphonate esters

Scheme 34. Nucleophilic desymmetrization at phosphorus (V)

Scheme 35. Ni-catalyzed synthesis of P-stereogenic phosphine-boranes

Scheme 36. Nickel-catalyzed synthesis of P-stereogenic phosphanyl hydrazine

Scheme 37. Iridium-catalyzed desymmetrization of phosphonamides at the N atom

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