金和手性磷酸共催化的不对称合成研究进展

doi:10.6023/cjoc202407033

摘要/Abstract

均相金催化在近年来发展迅速并取得了极大进展, 然而金(I)配合物的线性结构以及Au(III)有机配合物的不稳定性限制了其在很多不对称催化反应中的应用. 将金催化与有机催化结合起来, 能够实现优势互补, 大大拓展了不对称金催化的应用范围. 手性磷酸是一种结构独特的双功能有机催化剂, 其与过渡金属联合催化, 发展了很多单一催化剂难以实现的新反应. 综述了金和手性磷酸共催化进行不对称合成的研究进展, 从抗衡阴离子导向催化、协同催化和接力催化等三个方面进行了总结探讨, 并对其发展前景进行了展望.

关键词: 金催化, 手性磷酸, 阴离子导向催化, 协同催化, 接力催化

Homogeneous gold catalysis has developed rapidly and made great progress in recent years, however, the linear structure of Au(I) complexes and the instability of Au(III) organic complexes limit their application in many asymmetric catalytic reactions. Combining gold with organic small molecules as cocatalysts may promote complementary advantages and greatly expand the application scope of asymmetric gold catalysis. Chiral phosphoric acid is a kind of bifunctional organic catalyst with novel structure. Combining chiral phosphoric acids with transition metals can catalyze many new reactions that are difficult to realize with a single catalyst. The asymmetric reactions catalyzed by gold and chiral phosphoric acid are summarized from three aspects, including counter anion directed catalysis, cooperative catalysis and relay catalysis, as well as the latest research progress and development prospects are also discussed.

Key words: gold catalysis, chiral phosphoric acid, anion directed catalysis, cooperative catalysis, relay catalysis

引用此文

朱晓宇, 杨诗林, 罗宜铭, 李文泽. 金和手性磷酸共催化的不对称合成研究进展[J]. 有机化学, 2025, 45(4): 1178-1193.

Xiaoyu Zhu, Shilin Yang, Yiming Luo, Wenze Li. Advances of Asymmetric Synthesis Combining of Gold and Chiral Phosphoric Acid Catalysts[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1178-1193.

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图/表 41

图式1. 金属/有机小分子共催化的模式

Scheme 1. Modes of combining metal catalysis and organocatalysis

图式2. 金(I)-手性磷酸盐催化的不对称环化反应

Scheme 2. Enantioselective cyclization catalyzed by Au(I)- chiral phosphate

图式3. 单阳离子双核金配合物催化的手性四氢呋喃的合成

Scheme 3. Syntheis of chiral tetrahydrofurans catalyzed by mo- nocationic dinuclear gold complex

图式4. 亚甲基四氢吡咯衍生物的不对称合成

Scheme 4. Enantioselective synthesis of methylene pyrrolidines

图式5. 手性磷酸金催化喹啉的转移氢化反应

Scheme 5. Transfer hydrogenation of quinolines catalyzed by chiral gold phosphate

图式6. 四氢喹啉衍生物的不对称合成

Scheme 6. Enantioselective synthesis of tetrahydroquinoline derivatives

图式7. 金(I)连接抗衡阴离子导向催化的串联反应

Scheme 7. Au(I) tethered counterion-directed catalytic cascade reaction

图式8. 可能的催化机理

Scheme 8. Proposed catalytic mechanism

图式9. 1-萘酚与丙二烯胺的加成反应

Scheme 9. Addition of 1-naphthols with allenamides

图式10. 呋喃噁嗪和吡咯噁嗪衍生物的手性合成

Scheme 10. Enantioselective synthesis of furoxazines and pyrrolooxazines

图式11. 金(I)/胺/CPA共催化的串联反应

Scheme 11. Cascade reactions catalyzed by Au(I)/amine/CPA

图式12. 3-丁炔醇与硝酮的Mannich反应

Scheme 12. Mannich-type addition of 3-butynols and nitrone

图式13. 可能的协同催化机理

Scheme 13. Proposed cocatalytic mechanism

图式14. 端炔的立体选择性氧化多功能化

Scheme 14. Stereoselective oxidative muti-functionalization of terminal alkynes

图式15. 可能的协同催化机理

Scheme 15. Proposed cocatalytic mechanism

图式16. 甲苯的不对称C—H官能团化

Scheme 16. Enantioselective C—H functionalization of toluene

图式17. 内炔烃的不对称多功能化反应

Scheme 17. Enantioselective muti-functionalization of internal alkynes

图式18. 两种不同的催化机理

Scheme 18. Two different catalytic mechanisms

图式19. 金(I)催化的分子内氢胺化/手性磷酸催化的HEH反应

Scheme 19. Intramolecular hydroamination (AuI)/stereocontrolled HEH (CPA) cascade

图式20. 金(I)催化的分子内氢胺化/手性磷酸催化的HEH串联反应

Scheme 20. Consecutive intramolecular hydroamination (AuI) and stereocontrolled HEH (CPA)

图式21. 可能的接力催化机理

Scheme 21. Proposed relay catalytic mechanism

图式22. 聚环吲哚衍生物的不对称合成

Scheme 22. Enantioselective synthesis of polycyclic indole derivatives

图式23. 久洛利定衍生物的不对称合成

Scheme 23. Enantioselective synthesis of julolidine derivatives

图式24. 炔醇环化引发的与吖内酯的亲核加成

Scheme 24. Addition of azlactones triggered by cyclization of alkynols

图式25. 可能的催化机理

Scheme 25. Proposed catalytic mechanism

图式26. 金属/有机接力催化的聚环化合物的合成

Scheme 26. Metal/organo relay catalysis for synthesis of polycyclic compounds

图式27. 末端炔烃的还原胺化反应

Scheme 27. Reductive hydroamination of terminal alkynes

图式28. 1,2-二氢异喹啉稠环的不对称合成

Scheme 28. Enantioselective synthesis of fused 1,2-dihydroiso-quinolines

图式29. 四氢喹啉衍生物的不对称合成

Scheme 29. Enantioselective synthesis of tetrahydroquinoline derivatives

图式30. 金(I)/手性磷酸接力催化的redox-pinacol-Mannich反应

Scheme 30. Au(I)/CPA relay catalytic redox-pinacol-Mannich reaction

图式31. 金(I)/手性磷酸接力催化的环缩醛胺的合成

Scheme 31. Au(I)/CPA relay catalysis for the synthesis of cyclic aminals

图式32. 串联的氢烷氧化/Mannich类型/缩醛化反应

Scheme 32. Hydroalkoxylation/Mannich-type/acetalizaion cascade

图式33. 手性螺环缩醛的不对称合成

Scheme 33. Enantioselective synthesis of spiroacetals

图式34. 分子内氢胺化/N-磺酰亚胺环化串联反应

Scheme 34. Intramolecular hydroamination/N-sulfonyliminium cyclization cascade

图式35. δ-内酰胺的合成

Scheme 35. Application to δ-lactam synthesis

图式36. 六氢呋喃[3,2-c]喹啉的不对称合成

Scheme 36. Enantioselective synthesis of hexahydrofuro[3,2-c]quinolines

图式37. 炔醇的不对称氢胺化/氢芳基化反应

Scheme 37. Enantioselective hydroamination/hydroarylation of alkynols

图式38. 螺缩醛的不对称合成

Scheme 38. Enantioselective synthesis of spiroacetals

图式39. 四氢咔唑衍生物的不对称合成

Scheme 39. Enantioselective synthesis of tetrahydrocarbazole derivatives

图式40. 不对称的杂原子烯反应

Scheme 40. Enantioselective aza-ene-type reactions

图式41. 可能的催化机理

Scheme 41. Proposed catalytic mechanism

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