Recent Advances in Kinetic Resolution of Tertiary Alcohols

doi:10.6023/cjoc202110009

Abstract

Chiral tertiary alcohol is widely present in a series of bioactive compounds, natural products and pharmaceuticals. Consequently, the development of efficient asymmetric catalytic methods for their syntheses is highly important. Kinetic resolution (KR) is an important strategy to access enantioenriched alcohols from racemic alcohols. However, due to the requirement to distinguish three none-hydrogen substituents at the α-position of tertiary alcohols, it is challenging to develop highly efficient kinetic resolution protocols for tertiary alcohols with broad substrate scope. Nevertheless, significant progress has been made in the field of nonenzymatic kinetic resolution of tertiary alcohols in recent years, and a number of novel asymmetric reactions and catalytic systems have been successfully applied in the KR of tertiary alcohols. The tremendous advances in the kinetic resolution of tertiary alcohols are comprehensively reviewed, the substrate scope, characteristics, mechanisms and limitations of these methods are summarized, and our perspective on this research field is also provided.

Key words: chiral tertiary alcohols, asymmetric catalysis, kinetic resolution

Cite this article

Yunrong Chen, Wei Liu, Xiaoyu Yang. Recent Advances in Kinetic Resolution of Tertiary Alcohols[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 679-697.

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Fig. & Tab. 28

Figure 1. Natural products, drugs and chiral ligands containing chiral tertiary alcohol motifs

Scheme 1. Kinetic resolution and three strategies for kinetic resolution of tertiary alcohols

Scheme 2. Kinetic resolution of tertiary alcohols via peptides- catalyzed esterifications

Scheme 3. Kinetic resolution of tertiary alcohols via N-heterocyclic carbene-catalyzed acylation

Scheme 4. Kinetic resolution of heterocyclic tertiary alcohols via chiral Lewis base-catalyzed esterifications

Scheme 5. Kinetic resolution of acyclic tertiary alcohols via chiral Lewis base-catalyzed esterifications

Scheme 6. Kinetic resolution of heterocyclic tertiary alcohols via chiral DMAP derivative-catalyzed esterifications

Scheme 7. Kinetic resolution of tertiary propargylic alcohols via Cu-catalyzed Si-O coupling

Scheme 8. Kinetic resolution of homoaldols via chiral phosphoric acid catalyzed transacetalizations

Scheme 9. Kinetic resolution of diols via chiral confined imidodiphosphoric acid catalyzed acetalizations

Scheme 10. Kinetic resolution of tertiary alcohols via chiral phosphoric acid catalyzed cycloetherifications

Scheme 11. Kinetic resolution of tertiary 2-alkoxycarboxamido- substituted allylic alcohols by chiral phosphoric acid catalyzed intramolecular transesterifications

Scheme 12. Kinetic resolution of 2-amido tertiary benzyl alcohols by chiral phosphoric acid catalyzed intramolecular dehydrative condensations

Scheme 13. Kinetic resolution of 2-N-acylamido tertiary allylic alcohols by chiral phosphoric acid catalyzed intramolecular condensations

Scheme 14. Kinetic resolution of tertiary allylic alcohols by chiral phosphoric acid catalyzed cycloetherifications

Scheme 15. Kinetic resolution of tertiary benzyl alcohols via palladium/chiral norbornene cooperative catalysis

Scheme 16. Kinetic resolution of tertiary alcohols via organocatalyzed O-silylations of 1,2-diols

Scheme 17. Kinetic resolution of tertiary allylic alcohols through catalytic enantioselective epoxidations

Scheme 18. Alkylative kinetic resolution of 1,2-diols via chiral ammonium borinate catalysis

Scheme 19. Kinetic resolution of para-quinols via boronic-acid-directed chiral phosphoric acid catalyzed asymmetric oxa-Michael additions

Scheme 20. Kinetic resolution of auxiliary adjacent alcohols via chiral Lewis base-catalyzed esterifications

Scheme 21. Kinetic resolution of tertiary alcohols via chiral phosphoric acid catalyzed asymmetric enamide-imine tauto- merism

Scheme 22. Kinetic resolution of tertiary alcohols via Cu(I)-catalyzed azide-alkyne cycloadditions (CuAAC)

Scheme 23. Kinetic resolution of β-nitro tertiary alcohols via mixed La-Li heterobimetallic complexes catalysis

Scheme 24. Kinetic resolution of tertiary homoallyl alcohols via rhodium-catalyzed stereoselective carbon-carbon bond cleavage

Scheme 25. Kinetic resolution of tertiary propargylic alcohols through palladium/H+-cocatalyzed carboxylations

Scheme 26. Kinetic resolution of tertiary propargylic alcohols via rhodium-catalyzed asymmetric allenylations of benzamides

Scheme 27. Dynamic kinetic resolution of tertiary alcohol via cooperative catalysis of a lipase-catalyst & an oxovanadium catalyst

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