氮杂环卡宾/过渡金属联合催化研究进展

doi:10.6023/cjoc202106002

摘要/Abstract

氮杂环卡宾(NHC)催化在有机催化领域占有重要地位, 其催化的有机反应具有反应方式独特、反应位点丰富、底物和产物结构多样性等特点. 然而, 随着有机合成的深入发展, 传统的、单一的催化体系在底物反应活性及反应选择性方面也逐渐面临一些瓶颈和挑战. 近年来, 联合催化策略通过两种单一催化体系的有效结合, 能够实现单一催化体系无法实现的化学转化, 从而能够更好地实现反应性及反应选择性的精准调控, 逐渐成为有机合成中的重要催化策略. 主要综述了近十年来氮杂环卡宾/过渡金属联合催化方面的最新研究进展.

关键词: 氮杂环卡宾催化, 过渡金属催化, 联合催化, 不对称合成

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

引用此文

张建明, 高健, 冯捷, 陆涛, 杜鼎. 氮杂环卡宾/过渡金属联合催化研究进展[J]. 有机化学, 2021, 41(10): 3792-3807.

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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图/表 31

图式1. 氮杂卡宾键连的活性中间体

Scheme 1. NHC bound active intermediates

图式2. 氮杂环卡宾与过渡金属的配位与联合催化

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

图式3. 氮杂卡宾活化醛形成的Breslow中间体

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

图式4. 氮杂卡宾/钯联合催化下芳香醛的苯偶姻缩合-烯丙基化反应

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

图式5. 氮杂卡宾/钯协同催化的吡啶-2-甲醛的烯丙基化-异构化-Stetter串联反应

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

图式6. 氮杂卡宾/钯协同催化下脂肪醛的苄基化及烯丙基化反应

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

图式7. 氮杂卡宾/钯联合催化下脂肪醛的苄基化及烯丙基化反应的机理

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

图式8. 氮杂卡宾/钯联合催化下脂肪醛与烯丙醇、烯丙胺的偶联反应

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

图式9. 氮杂卡宾/钯联合催化的吡啶-2-甲醛的炔丙基化反应

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

图式10. 氮杂卡宾催化活化烯醛形成的高烯醇盐中间体及其反应活性

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

图式11. 氮杂卡宾/钯联合催化的基于高烯醇盐的不对称[4+3]环合反应

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

图式12. 氮杂卡宾/钯联合催化的不对称[4+3]环合反应机理

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

图式13. 氮杂卡宾/钯联合催化的不对称[4+1]环合反应

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

图式14. 氮杂卡宾/铜联合催化的高烯醇盐参与的环合反应

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

图式15. 氮杂卡宾/铜联合催化下基于高烯醇盐中间体的[3+3]环合反应机理

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

图式16. 氮杂卡宾/铜联合催化的消旋2-苯基-N-对甲基苯磺酰基吖啶的动力学拆分

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

图式17. 氮杂卡宾/钯联合催化的烯醛的β-芳基化反应

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

图式18. 氮杂卡宾/钯联合催化下烯醛β-芳基化的反应机理

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

图式19. 氮杂卡宾键连的烯醇盐中间体

Scheme 19. NHC bound enolates intermediates

图式20. 氮杂卡宾/钯联合催化的烯醛分子内α-烯丙基化-氧酰基化串联反应

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

图式21. 氮杂卡宾/钯联合催化的烯醛分子内α-烯丙基化-氧酰基化串联反应的机理

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

图式22. 氮杂卡宾/钯协同催化的基于烯醇盐的不对称[5+2]环合反应(NMPi: N-methylpiperidine)

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

图式23. 氮杂卡宾/铱协同催化的基于烯醇盐的不对称[3+2]环合反应(NMM, N-methylmorpholine)

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

图式24. 氮杂卡宾/铱协同催化的基于烯醇盐的不对称[3+2]环合反应机理

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

图式25. 氮杂卡宾/铱协同催化的不对称[3+2]及[3+3]环合反应

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

图式26. 氮杂卡宾/金联合催化的不对称Diels-Alder反应及机理

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

图式27. 氮杂卡宾键连的烯基烯醇盐

Scheme 27. NHC bound vinyl enolates

图式28. 氮杂卡宾/钯联合催化的基于烯基烯醇盐的[3+2]环合反应

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

图式29. 氮杂卡宾/钯联合催化的基于烯基烯醇盐的[3+2]环合反应机理

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

图式30. 氮杂卡宾/铜联合催化的三组分反应

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

图式31. 氮杂卡宾/钯联合催化的2,3-苯并二氮?化合物骨架的不对称构建

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

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