吡啶鎓1,4-两性离子硫醇盐在有机合成中的应用

doi:10.6023/cjoc202511005

摘要/Abstract

近年来, 吡啶鎓1,4-两性离子硫醇盐及其喹啉鎓与异喹啉鎓类似物作为新型多功能合成子, 在合成化学领域展现出广泛的应用价值. 该类化合物凭借优异的空气稳定性、无特殊气味以及易于制备与储存等优势, 受到合成化学家的普遍关注. 系统综述了吡啶鎓1,4-两性离子硫醇盐及其喹啉鎓与异喹啉鎓类似物的研究进展, 重点讨论其在有机转化中的应用, 一方面可作为关键合成子参与[3＋m]和[5＋m]环合反应以构建杂环骨架, 另一方面也可作为硫原子转移试剂将异腈转化为异硫氰酸酯. 这些高选择性、多样化的反应模式, 为精准合成结构多样的含氮和/或硫化合物提供了高效策略, 展现了其在复杂分子合成中的巨大潜力.

关键词: 吡啶鎓1,4-两性离子硫醇盐, 氮杂环分子, 硫杂环分子, 串联反应

Pyridinium 1,4-zwitterionic thiolates and their quinolinium/isoquinolinium analogs have recently emerged as novel multifunctional synthons with broad synthetic utility. These compounds have attracted wide synthetic interest for being air-stable, odorless, easy-to-handle and readily available. In this review, the advances in pyridinium 1,4-zwitterionic thiolates and their quinolinium/isoquinolinium analogs for organic transformations are summarized: as key synthons for heterocycle construction via formal [3＋m] and [5＋m] annulations, and as sulfur-transfer reagent to convert isocyanides to isothiocyanates. These methods provide efficient access to diverse nitrogen- and/or sulfur-containing scaffolds, enabling efficient synthesis of structurally diverse molecules.

Key words: pyridinium 1,4-zwitterionic thiolate, nitrogen-containing heterocycle, sulfur-containing heterocycle, cascade reaction

引用此文

王文博, 陈贵川, 王锦博, 赵阳, 王琪琳. 吡啶鎓1,4-两性离子硫醇盐在有机合成中的应用[J]. 有机化学, 2026, 46(5): 1845-1870.

Wenbo Wang, Guichuan Chen, Jinbo Wang, Yang Zhao, Qilin Wang. Applications of Pyridinium 1,4-Zwitterionic Thiolates in Organic Synthesis[J]. Chinese Journal of Organic Chemistry, 2026, 46(5): 1845-1870.

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图/表 32

图式1. PZTs的不同反应模式

Scheme 1. Diverse reaction modes of PZTs

图式2. PZTs参与的[3＋m]反应示例

Scheme 2. Representative [3＋m] reaction with PZTs

图式3. PZTs参与的[3＋4]及[(3＋3)－1]环合反应

Scheme 3. [3＋4] and [(3＋3)－1] annulation reaction of PZTs

图式4. 选择性合成4,1-苯并硫氮杂䓬衍生物

Scheme 4. Selective synthesis of 4,1-benzothiapine derivatives

图式5. 合成芳环稠合1,4-氧硫杂䓬化合物

Scheme 5. Synthesis of aryl-fused 1,4-oxathiepines

图式6. PZTs参与的[3＋3]环合反应

Scheme 6. [3＋3] annulation of PZTs

图式7. 利用[3＋3]反应构建1,4-氧硫杂环骨架

Scheme 7. [3＋3] annulation for the formation of 1,4-oxathiin scaffolds

图式8. 利用环合反应构建稠杂环分子

Scheme 8. Annulation reaction to construct polycyclic heterocycles

图式9. PZTs用于合成含硫螺环氧化吲哚

Scheme 9. Synthesis of S-containing spirooxindoles using PZTs

图式10. 2-三氟甲基噻唑的合成

Scheme 10. Synthesis of 2-trifluoromethyl thiazoles

图式11. 合成取代吡咯衍生物

Scheme 11. Synthesis of substituted pyrrole derivatives

图式12. PZTs参与的[3＋2]环合串联反应

Scheme 12. [3＋2] cascade annulation reaction of PZTs

图式13. PZTs与联烯衍生物参与的串联环化反应

Scheme 13. Cascade annulation between PZTs and activated allenes

图式14. PZTs参与的光化学转化

Scheme 14. Photochemical transformation of PZTs

图式15. 磺酰基取代噻吩化合物的合成

Scheme 15. Methods for the preparation of sulfonylthiophenes

图式16. 可能的反应机理

Scheme 16. Possible reaction mechanism

图式17. PZTs参与的[5＋m]反应示例

Scheme 17. Representative [5＋m] reaction of PZTs

图式18. PZTs与α-官能团化的溴代烷烃参与的串联反应

Scheme 18. Cascade reaction between PZTs and α-functionalized bromoalkanes

图式19. PZTs与丙炔酸衍生物反应合成吲嗪类化合物

Scheme 19. Synthesis of indolizines from PZTs and propiolic acid derivatives

图式20. PZTs与重氮化合物之间的环化反应

Scheme 20. Annulation reaction between PZTs and diazo compounds

图式21. PZTs与二氟卡宾参与的[5＋1]环合反应

Scheme 21. [5＋1] annulation of PZTs with difluorocarbene

图式22. PZTs与氧化锍叶立德参与的[(5＋1)－1]环合反应

Scheme 22. [(5＋1)－1] annulation of PZTs with sulfoxonium ylides

图式23. 经逐步的[(5＋1)-1]途径合成吲嗪衍生物

Scheme 23. A synthetic route to indolizines via a step [(5＋1)-1] pathway

图式24. PZTs用于合成多稠杂环化合物

Scheme 24. Synthesis of fused polyheterocycles using PZTs

图式25. 喹啉鎓硫醇盐参与的串联环合反应

Scheme 25. Cascade annulation reaction of quinolinium thiolates

图式26. 发散合成两种新型硫氮杂环化合物

Scheme 26. Divergent synthesis of two new N,S-heterocycles

图式27. 合成苯并硫氮杂䓬衍生物及苯并噻吩衍生物

Scheme 27. Synthesis of benzopyridothiazepines and benzothiophenes

图式28. PZTs与砜烯衍生物参与的两类环合反应

Scheme 28. Two annulation reactions of PZTs and sulfenes

图式29. PZTs与三唑化合物之间的两种反应模式

Scheme 29. Two reaction modes of PZTs and 1-sulfonyl-1,2,3-triazoles

图式30. PZTs与膦酰基卡宾参与不同反应模式

Scheme 30. Different reaction modes of PZTs and phosphorylcarbenes

图式31. 发散式合成含硫原子的桥环环丁烷衍生物

Scheme 31. Divergent synthesis of sulfur-containing bridged cyclobutanes

图式32. 以PZTs为硫源合成异硫氰酸酯化合物

Scheme 32. Synthesis of isothiocyanates by PZTs as a sulfur source

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