三芳基碳正离子在有机合成中的应用

doi:10.6023/cjoc202308007

摘要/Abstract

三芳基碳正离子作为一种优异的路易斯酸, 其最低空分子轨道(LUMO)轨道能级较低, 易接受一对电子, 被广泛应用于合成转化中, 是重要的试剂和催化剂. 近年来, 三芳基碳正离子在有机合成中主要被用作催化剂、预催化剂、共催化剂和添加剂. 此外, 三芳基碳正离子作为关键中间体, 可以成功应用于四芳基甲烷的合成. 综述了近年来三芳基碳正离子在有机合成中的应用进展, 并总结了三芳基碳正离子在有机合成中的多种功能作用, 希望引起广泛的关注.

关键词: 三芳基碳正离子, 催化剂, 有机合成, 无金属

Triaryl carbenium, known as an exceptional Lewis acid, possesses a low-lying lowest unoccupied molecular orbital (LUMO) that readily accepts an electron pair, which was widely used in synthetic transformations serving as reagent or catalyst. Over the past decade, triaryl carbenium has been used as catalyst, pre-catalyst, co-catalyst and additive in organic synthesis. Moreover, triaryl carbenium as a key intermediate approached to the successful synthesis of tetra-arylmethane. In this review, the application progress of triaryl carbenium in organic synthesis in recent years is summarized, and its diverse functional roles in organic synthesis are summarized, hoping to attract widespread attention.

Key words: triaryl carbenium, catalysis, organic synthesis, metal-free

引用此文

李路瑶, 贺忠文, 张振国, 贾振华, 罗德平. 三芳基碳正离子在有机合成中的应用[J]. 有机化学, 2024, 44(2): 421-437.

Luyao Li, Zhongwen He, Zhenguo Zhang, Zhenhua Jia, Teck-Peng Loh. Application of Triaryl Carbenium in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 421-437.

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图/表 31

图式1. [Tr]＋[BF4]—催化狄尔斯-阿尔德反应和迈克尔加成反应[10]

Scheme 1. [Tr]＋[BF4]—-catalyzed Diels-Alder and Michael addition reactions[10]

图式2. Franzén课题组[Tr]＋[BF4]—催化有机转化[11]

Scheme 2. Franzén’s [Tr]＋[BF4]—-catalyzed organic transformations[11]

图式3. [Tr]＋[BF4]—催化氧杂狄尔斯-阿尔德反应和氧杂复分解反应[12-13]

Scheme 3. [Tr]＋[BF4]—-catalyzed oxa-Diels-Alder and oxo-Metathesis reactions[12-13]

图式4. [Tr]＋[BF4]—催化芳烃溴代反应[14]

Scheme 4. [Tr]＋[BF4]— catalyzed bromination of arenes[14]

图式5. [Tr]＋[BF4]—催化1,2-氢迁移和1,6-加成反应[15-16]

Scheme 5. [Tr]＋[BF4]—?catalyzed 1,2-hydride migration and 1,6-addition reactions[15-16]

图式6. [Tr]＋[BF4]—催化环加成和开环反应[17??-20]

Scheme 6. [Tr]＋[BF4]—?catalyzed cycloaddition and ring-opening reactions[17??-20]

图式7. 三芳基碳正离子对催化分子内羰基烯环化反应和[2＋2]环加成反应[21]

Scheme 7. Triaryl carbenium ion-pair catalyzed intramolecular carbonyl-ene cyclization and [2＋2] cycloaddition reactions[21]

图式8. [Tr]＋[B(C6F5)4]—催化蒽衍生物参与的狄尔斯-阿尔德反应[22]

Scheme 8. [Tr]＋[B(C6F5)4]— catalyzed Diels-Alder reaction with anthracene derivatives[22]

图式9. [Tr]＋[B(C6F5)4]—催化分子间[2＋2＋1]环加成反应[23]

Scheme 9. [Tr]＋[B(C6F5)4]— catalyzed intermolecular formal [2＋2＋1] cycloaddition reaction[23]

图式10. [Tr]＋[B(C6F5)4]—催化烯烃加氢芳基化和Hosomi-Sakurai反应[24-25]

Scheme 10. [Tr]＋[B(C6F5)4]— catalyzed hydroarylation of alkenes and Hosomi-Sakurai reaction[24-25]

图式11. 手性磷酸三酯原位生成三芳基碳正离子对催化不对称反应[27]

Scheme 11. In-situ synthesis of triaryl carbenium from chiral triphosphate catalyzed asymmetric reactions[27]

图式12. 三苯基碳正离子在蒽不对称Diels-Alder反应中的应用[28]

Scheme 12. Application of triaryl carbenium in the asymmetric Diels-Alder reaction of anthracene[28]

图式13. β-苄基苯乙烯的分子内加氢芳基化反应[29]

Scheme 13. Intramolecular hydroarylation of β?benzylstyrenes[29]

图式14. 分子间碳氢插入反应[30]

Scheme 14. Intermolecular C—H insertion reaction[30]

图式15. 分子内碳氢插入反应[31]

Scheme 15. Intramolecular C—H insertion reaction[31]

图16. [Tr]＋[B(C6F5)4]—作预催化剂催化水相中Friedel-Crafts反应和Pictet-Spengler反应[32-33]

Scheme 16. Friedel-Crafts and Pictet-Spengler reactions used [Tr]＋[B(C6F5)4]— as pre-catalyst in water[32-33]

图式17. [Tr]＋[B(C6F5)4]—作预催化剂合成β-咔啉[34]

Scheme 17. Synthesis of β-carbolines used [Tr]＋[B(C6F5)4]— as pre-catalyst[34]

图式18. [Tr]＋[B(C6F5)4]—与钇协同催化N,N-二甲基苯胺的邻位选择性碳氢烷基化反应[36]

Scheme 18. [Tr]＋[B(C6F5)4]—-combined with yttrium catalyzed ortho-selective C—H alkylation of N,N-dimethyl anilines[36]

图式19. [Tr]＋[B(C6F5)4]—与钇协同催化2-甲基氮杂芳烃C(sp3)—H键活化反应[37]

Scheme 19. [Tr]＋[B(C6F5)4]—-combined with yttrium catalyzed C(sp3)—H activation of 2-methyl azaarenes[37]

图式20. [Tr]＋[B(C6F5)4]—引发炔基苯基硅烷分子内硅氢化反应[38]

Scheme 20. [Tr]＋[B(C6F5)4]— initiated intramolecular hydrosilylation of alkynylphenylsilanes[38]

图式21. [Tr]＋[B(C6F5)4]—引发锡氢化反应[39]

Scheme 21. [Tr]＋[B(C6F5)4]— initiated hydrostannylation[39]

图式22. [Tr]＋[B(C6F5)4]—引发Friedel-Crafts烷基化和环化反应[40-41]

Scheme 22. [Tr]＋[B(C6F5)4]— initiated Friedel-Crafts alkylation and annulation reaction[40-41]

图式23. [Tr]＋[B(C6F5)4]—引发1,1-二氟烯烃的Friedel-Crafts型环化反应[42]

Scheme 23. [Tr]＋[B(C6F5)4]— initiated intramolecular Friedel- Crafts-type cyclization of 1,1-difluoroalkenes[42]

图式24. [Tr]＋[B(C6F5)4]—引发合成膦类化合物[43]

Scheme 24. Synthesis of phosphine compounds initiated by [Tr]＋[B(C6F5)4]—[43]

图式25. Ph3C＋[B(C6F5)4]—作预催化剂催化酮的无金属氰基硅烷化反应[44]

Scheme 25. Metal-free cyanosilylation of ketones used Ph3C＋[B(C6F5)4]— as pre-catalyst[44]

图式26. 三苯基碳正离子对参与辅助合成三芳基甲烷[45]

Scheme 26. Synthesis of triarylmethane using triaryl carbenium ion-pair as co-catalyst[45]

图式27. [Tr]＋[BF4]—介导的C—F单键裂解反应[46]

Scheme 27. [Tr]＋[BF4]—-mediated single C—F bond cleavage reaction[46]

图式28. [Tr]＋[BF4]—介导的C—F单键裂解合成二氟亚甲基化合物[47]

Scheme 28. [Tr]＋[BF4]—-mediated single C—F bond cleavage reaction for the synthesis of difluoromethylenes[47]

图式29. 通过三芳基碳正离子中间体不对称合成四芳基甲烷类化合物[48]

Scheme 29. Asymmetric synthesis of tetraarylmethanes via triaryl carbenium intermediates[48]

图式30. 通过三芳基碳正离子中间体实现三芳基甲醇与吲哚之间的不对称取代反应[49]

Scheme 30. Asymmetric substitution reaction of triaryl methanol with indoles via triaryl carbenium intermediates[49]

图式31. 三芳基甲醇的不对称取代反应[50]

Scheme 31. Asymmetric substitution reaction of triaryl methanol[50]

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