Recent Advances in Synthesis of Chiral Tertiary Amines via Asymmetric Catalysis Involving Metal-Hydride Species

doi:10.6023/cjoc202206032

Abstract

Chiral tertiary amines, as a class of important skeleton, exist in various drugs, natural products, and organic functional materials. Therefore, the development of efficient synthetic methods for the preparation of chiral tertiary amines has attracted much attention from chemists and become one of the research hotspots in recent years. Until now, several asymmetric catalytic methods involving metal-hydride species have been developed. According to different reaction types, the research progress in recent years is summarized from four aspects: asymmetric hydroamination, asymmetric hydrogenation, asymmetric reductive amination, and asymmetric amination of alcohols via the ‘borrowing hydrogen’ strategy. At the same time, the corresponding reaction mechanism of each strategy is introduced, and the future development of this field is envisioned.

Key words: tertiary amine, asymmetric catalysis, metal-hydride species, hydrogenation, hydroamination

Cite this article

Tianxiang Fan, Yuanyuan Liu. Recent Advances in Synthesis of Chiral Tertiary Amines via Asymmetric Catalysis Involving Metal-Hydride Species[J]. Chinese Journal of Organic Chemistry, 2022, 42(10): 3280-3294.

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Fig. & Tab. 41

Figure 1. Chiral amine drugs

Scheme 1. Asymmetric catalytic synthesis of chiral amines

Scheme 2. Copper-catalyzed asymmetric hydroamination of olefins

Scheme 3. Copper-catalyzed asymmetric hydroamination of vinylsilanes

Scheme 4. Copper-catalyzed asymmetric hydroamination of unactivated internal alkenes

Scheme 5. Directing group-directed copper-catalyzed asymmetric hydroamination of disubstituted olefins

Scheme 6. Asymmetric hydroamination of boron- and phosphine-functionalized olefins

Scheme 7. Copper-catalyzed asymmetric hydroamination of 1- trifluoromethylalkenes

Scheme 8. Synthesis of 1,2-diamine by asymmetric hydroamination

Scheme 9. Synthesis of γ-amino alcohols by asymmetric hydroamination

Scheme 10. Copper-catalyzed hydroamination of strained trisubstituted alkenes

Scheme 11. Copper-catalyzed asymmetric hydroamination of 2H-benzopyranes

Scheme 12. Rhodium-catalyzed asymmetric hydroamination of allyl imines to 1,2-diamines

Scheme 13. Rhodium-catalyzed asymmetric hydroamination of alkynes and allenes

Scheme 14. Mechanism of rhodium-catalyzed asymmetric hydroamination

Scheme 15. Rhodium-catalyzed intramolecular hydroamination of internal alkynes and allenes

Scheme 16. Rhodium-catalyzed asymmetric hydroamination of conjugated dienes

Scheme 17. Palladium-catalyzed asymmetric hydroamination of 1,3-conjugated dienes

Scheme 18. Mechanism of palladium-catalyzed asymmetric hydroamination of conjugated diene

Scheme 19. Palladium-catalyzed asymmetric hydroamination of disubstituted internal conjugated dienes

Scheme 20. Mechanism of asymmetric hydroamination of internal conjugated diene catalyzed by palladium

Scheme 21. Palladium-catalyzed asymmetric hydroamination of dienes with pyrazoles

Scheme 22. Nickel-catalyzed asymmetric hydroamination of secondary amine with branched dienes

Scheme 23. Mechanism of asymmetric hydroamination of diene with secondary amine catalyzed by nickel

Scheme 24. Nickel-catalyzed asymmetric hydroamination of linear dienes with secondary amine

Scheme 25. Ti-catalyzed synthesis of chiral tertiary amine by asymmetric hydrogenation

Scheme 26. Synthesis of chiral tertiary amine by ruthenium- catalyzed asymmetric hydrogenation

Scheme 27. Rhodium-catalyzed asymmetric hydrogenation of unfunctionalized enamines

Scheme 28. Rhodium-catalyzed asymmetric hydrogenation of endo-cyclic enamines

Scheme 29. Rhodium-catalyzed asymmetric hydrogenation of exo-cyclic enamines

Scheme 30. Mechanism of rhodium-catalyzed asymmetric hydrogenation of exo-cyclic enamines

Scheme 31. Iridium-catalyzed asymmetric hydrogenation of enamine

Scheme 32. Iridium-catalyzed asymmetric hydrogenation of cyclic imine salts

Scheme 33. Iridium-catalyzed asymmetric reductive amination reaction

Scheme 34. Rhodium-catalyzed asymmetric reductive amination reaction

Scheme 35. Ruthenium-catalyzed asymmetric cascade reaction involving reductive amination

Scheme 36. Ruthenium-catalyzed cascade reaction involving reductive amination

Scheme 37. Reaction mechanism of borrowing hydrogen strategy

Scheme 38. Synthesis of chiral piperidine by borrowing hydrogen strategy

Scheme 39. Mechanism of piperidine synthesis by borrowing hydrogen strategy

Scheme 40. Synthesis of piperidine alkaloids by borrowing hydrogen strategy

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