Recent Progress in Catalytic Asymmetric Alkynylation of Imines

doi:10.6023/cjoc202007043

Abstract

Chiral propargyl amines are key intermediates in the asymmetric total synthesis of natural products and bioactive compounds. The asymmetric alkynylation of imine and its analogues can provide a highly efficient and enantioselective synthetic route for these chiral building blocks. In addition, through rational substrate and reaction design, the asymmetric alkynylation of imines can be used as the starting point of a series of cascade reactions to synthesize a variety of novel nitrogen-heterocyclic compounds. Therefore, highly efficient and enantioselective alkynylation of imines and their analogues has attracted the continuous attention of synthetic chemists. According to the types of substrate, the research progress in asymmetric alkynylation of imines and their analogues over the past decade is introduced, which is divided into two parts: asymmetric alkynylation of aldimines and asymmetric alkynylation of ketoimines. The reaction mechanism and their advantages and disadvantages, together their synthetic applications will be briefly introduced, hoping to provide some useful inspiration for expanding the application of this reaction in synthesis.

Key words: chiral propargyl amine, asymmetric alkynylation, aldimine, ketoimine, nitrogen-heterocyclic compound

Cite this article

Shurui Zhou, Kaige Wen, Xingping Zeng. Recent Progress in Catalytic Asymmetric Alkynylation of Imines[J]. Chinese Journal of Organic Chemistry, 2021, 41(2): 471-489.

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Fig. & Tab. 43

Scheme 1. Asymmetric alkylation of imines

Scheme 2. Tridentate ligand catalyzed asymmetric alkynylation

Scheme 3. Enantioselective alkylation catalyzed by 3,3'-di- bromo-BINOL complex

Scheme 4. Enantioselective alkylation of N-sulfonyl aldimines

Scheme 5. Enantioselective alkynylation of in situ generated aldimines

Scheme 6. Enantioselective cross-dehydrogenative coupling of N-aryl glycine esters with terminal alkynes

Scheme 7. Asymmetric alkynylation derived cascade reactions

Scheme 8. Asymmetric alkynylation of C,N-cyclic azomethine imines

Scheme 9. Asymmetric copper-catalyzed quinoline alkynylation

Scheme 10. Asymmetric dearomative alkynylation of isoquinolines

Scheme 11. Asymmetric alkynylation of 7-membered cyclic imine

Scheme 12. Asymmetric alkynylation of benzo[e][1,2,3]-oxa- thiazine 2,2-dioxides

Scheme 13. Diarylprolinol as a ligand for enantioselective alkynylation

Scheme 14. Asymmetric alkynylation in a ball mill

Scheme 15. Enantioselective catalytic cross-dehydrogenative coupling (CDC) of N-carbamoyl tetrahydroisoquinolines and terminal alkynes

Scheme 16. Enantioselective alkynylation of tetrahydroisoquinoline based N-acyl hemiaminals

Scheme 17. Synergistic photocatalytic and copper-catalyzed CDC reaction between tertiary amines and terminal alkynes

Scheme 18. Bimetallic cooperatively catalyzed cross-dehydro- genative coupling (CDC) reaction

Scheme 19. Cascade asymmetric alkynylation/lactamization to enantiomerically enriched isoindolinones

Scheme 20. Cascade reactions based on asymmetric A3 reaction

Scheme 21. Asymmetric A3 reaction under ball-milling conditions

Scheme 22. Tandem asymmetric A3 coupling-carboxylative cyclization sequence to 2-oxazolidinones

Scheme 23. Chiral bis(imidazoline)-Cu(I) catalyzed A3 reaction

Scheme 24. Chiral bis(imidazoline)-Cu(I) complex catalyzed A3 reaction in water

Scheme 25. Synthesis of chiral allenes from terminal alkynes

Scheme 26. (R,R)-N-PINAP-Cu(I) complex catalyzed A3 reaction

Scheme 27. Synthesis of chiral N-allyl pyrrole from alkynes

Scheme 28. Tetrahydroisoquinoline based asymmetric A3 reaction and its application

Scheme 29. Asymmetric total syntheses of 13-methyltetrahy- droprotoberberine alkaloids

Scheme 30. Chiral stackPhos-Cu(I) complex catalyzed enantioselective A3 reaction and its application

Scheme 31. Chiral stackPhim-Cu(I) complex catalyzed asymmetric A3 reaction

Scheme 32. Asymmetric A3 reaction enabled by synergistic Br?nsted acids and Cu(I) catalysis

Scheme 33. First highly enantioselective alkynylation of α- ketoimine ester

Scheme 34. Zn-BINOL catalyzed highly enantioselective alkynylations

Scheme 35. Phebox-Rh catalyzed highly enantioselective alkynylation of α-ketoimine ester

Scheme 36. (Alkynyl)rhodium(III) complexes catalyzed highly enantioselective alkynylation

Scheme 37. Catalytic asymmetric alkynylation of acyclic ketoimines derived from simple ketones

Scheme 38. Total synthesis of drug molecule KAE069

Scheme 39. Asymmetric alkynylation of isatin-derived ketimines

Scheme 40. Catalytic asymmetric alkynylation of 1-alkyl C,N- cyclic azomethine imines

Scheme 41. Cu-catalyzed enantioselective alkynylation of α,α-diaryl ketimines

Scheme 42. Catalytic asymmetric alkynylation of cyclic N-acyl trifluoromethyl ketimines

Scheme 43. Asymmetric alkynylation of cyclic N-sulfonyl ketimines

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