Recent Advances in Synergistic Catalysis by Merging N-Heterocyclic Carbenes and Transition Metals

doi:10.6023/cjoc202106002

Abstract

Unique reaction modes, diverse reaction sites, and structural diversity of both substrates and products have made N-heterocyclic carbene catalysis be of great of importance in the field of organic catalysis. However, there have been a lot of barriers and challenges in terms of the reactivity of substrates and the selectivity of reactions for traditional and single catalytic systems with the deep development of organic synthesis. Recently, synergistic catalysis makes it possible for previously inaccessible transformations and can adjust the reactivity and selectivity more accurately by merging two single catalytic systems, thus has emerged as a powerful catalytic strategy in organic synthesis. In this review, the latest research progress in the field of synergistic catalysis of N-heterocyclic carbenes and transition metals in the last decade is mainly reviewed.

Key words: N-heterocyclic carbene catalysis, transition metal catalysis, synergistic catalysis, asymmetric synthesis

Cite this article

Jianming Zhang, Jian Gao, Jie Feng, Tao Lu, Ding Du. Recent Advances in Synergistic Catalysis by Merging N-Heterocyclic Carbenes and Transition Metals[J]. Chinese Journal of Organic Chemistry, 2021, 41(10): 3792-3807.

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Fig. & Tab. 31

Scheme 1. NHC bound active intermediates

Scheme 2. Coordination and synergistic catalysis of NHCs and transition metals

Scheme 3. NHC bound Breslow intermediate via the activation of aldehydes

Scheme 4. NHC/Pd co-catalyzed benzoin condensation-allylation of aromatic aldehydes

Scheme 5. Tandem allylation-isomerization-Stetter reaction of pyridine-2-carboxaldehyde by NHC/Pd synergistic catalysis

Scheme 6. NHC/Pd co-catalyzed benzylation and allylation of aliphatic aldehydes

Scheme 7. Mechanism of benzylation and allylation of aliphatic aldehydes via NHC/Pd synergistic catalysis

Scheme 8. Allylation of aliphatic aldehydes with allylic alcohols and allylic amines by NHC/Pd co-catalysis

Scheme 9. NHC/Pd co-catalyzed propargylation of pyridine- 2-carboxaldehydes

Scheme 10. Generation and activity of homoenolates from enals activated by NHC-catalysis

Scheme 11. NHC/Pd co-catalyzed enantioselective [4+3] annulation reaction of homoenolates

Scheme 12. Mechanism of enantioselective [4+3] annulation reaction by NHC/Pd synergistic catalysis

Scheme 13. NHC/Pd co-catalyzed enantioselective [4+1] annulation reaction

Scheme 14. NHC/Cu co-catalyzed annulation reactions involved NHC bound homoenolates

Scheme 15. Mechanism of the [3+3] annulation reaction involved NHC bound homoenolates by NHC/Cu co-catalysis

Scheme 16. Kinetic resolution of N-tosyl-2-phenylaziridine by synergistic NHC/Cu catalysis

Scheme 17. β-Arylation of enals by NHC/Pd co-catalysis

Scheme 18. Reaction mechanism of β-arylation of enals by NHC/Pd co-catalysis

Scheme 19. NHC bound enolates intermediates

Scheme 20. NHC/Pd co-catalyzed intramolecular tandem α- allylation and O-acylation reaction of enals

Scheme 21. Mechanism of NHC/Pd co-catalyzed intramolecular tandem α-allylation and O-acylation reaction of enals

Scheme 22. Asymmetric [5+2] annulation reaction involved enolates by NHC/Pd synergistic catalysis (NMPi: N-methylpiperidine)

Scheme 23. Asymmetric [3+2] annulation reaction involved enolates by NHC/Ir synergistic catalysis (NMM, N-methylmorpholine)

Scheme 24. Mechanism of asymmetric [3+2] annulation reaction involved enolates by NHC/Ir synergistic catalysis

Scheme 25. Asymmetric [3+2] and [3+3] annulation reactions co-catalyzed by NHC/Ir

Scheme26. NHC/Au co-catalyzed asymmetric Diels-Alder reaction and the mechanism

Scheme 27. NHC bound vinyl enolates

Scheme 28. Synergistic NHC/Pd catalyzed [3+2] annulation of vinyl enolates

Scheme 29. Reaction mechanism of the [3+2] annulation involved vinyl enolates by synergistic NHC/Pd catalysis

Scheme 30. NHC/Cu co-catalyzed three-component reaction

Scheme 31. Asymmetric construction of 2,3-benzodiazepines skeletons by NHC/Pd synergistic catalysis

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