Applications of Pyridinium 1,4-Zwitterionic Thiolates in Organic Synthesis

doi:10.6023/cjoc202511005

Abstract

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

Cite this article

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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Fig. & Tab. 32

Scheme 1. Diverse reaction modes of PZTs

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

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

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

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

Scheme 6. [3＋3] annulation of PZTs

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

Scheme 8. Annulation reaction to construct polycyclic heterocycles

Scheme 9. Synthesis of S-containing spirooxindoles using PZTs

Scheme 10. Synthesis of 2-trifluoromethyl thiazoles

Scheme 11. Synthesis of substituted pyrrole derivatives

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

Scheme 13. Cascade annulation between PZTs and activated allenes

Scheme 14. Photochemical transformation of PZTs

Scheme 15. Methods for the preparation of sulfonylthiophenes

Scheme 16. Possible reaction mechanism

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

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

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

Scheme 20. Annulation reaction between PZTs and diazo compounds

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

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

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

Scheme 24. Synthesis of fused polyheterocycles using PZTs

Scheme 25. Cascade annulation reaction of quinolinium thiolates

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

Scheme 27. Synthesis of benzopyridothiazepines and benzothiophenes

Scheme 28. Two annulation reactions of PZTs and sulfenes

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

Scheme 30. Different reaction modes of PZTs and phosphorylcarbenes

Scheme 31. Divergent synthesis of sulfur-containing bridged cyclobutanes

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

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吡啶鎓1,4-两性离子硫醇盐在有机合成中的应用