异硫氰酸盐合成与应用的最新进展

doi:10.6023/cjoc202410008

摘要/Abstract

异硫氰酸盐(ITCs)是一类重要的有机化合物, 其特征是有R—N=C=S官能团. 异硫氰酸盐官能团广泛存在于天然产物和药物分子中, 由于其高反应活性和用途多样性, 被广泛用作有机合成的中间体. 综述了从胺类、异氰化物、叠氮化物等富氮原材料和肟类化合物出发合成ITCs的方法, 还将涵盖其在有机化合物合成中作为中间体的应用. 未来的研究或将聚焦于优化多功能异硫氰酸酯的合成工艺、解析其复杂的生物作用机制, 同时探索新的应用场景, 以此凸显异硫氰酸酯在现代化学与生物技术领域的持续重要性.

关键词: 异硫氰酸酯, 伯胺, 异氰化物, 叠氮化物, 异氰酸酯, 环加成反应

Isothiocyanates (ITCs) are an important class of organic compounds characterized by the functional group R—N= C=S. These functional groups are widely found in multiple natural products and pharmaceutical important drugs. Moreover, due to their high and versatile reactivity, they are widely used as an intermediate in organic synthesis. Keeping in view ITCs importance, this review summarizes their synthesis from nitrogen rich raw materials like amines, isocyanides, azides and some other compounds like oximes. Besides their synthesis, their application in organic compound synthesis as an intermediate will also be covered. Future research will likely focus on optimizing the synthesis of multifunctional isothiocyanates, understanding their complex biological mechanisms, exploring new applications, and highlighting the continued importance of isothiocyanates in modern chemistry and biotechnology.

Key words: isothiocyanates, primary amines, isocyanides, azide, isocyanates, cycloaddition

引用此文

刘尊棋, Jahangir Khan, Muhammad Akram, Yasir Mumtaz. 异硫氰酸盐合成与应用的最新进展[J]. 有机化学, 2025, 45(7): 2350-2366.

Zunqi Liu, Jahangir Khan, Muhammad Akram, Yasir Mumtaz. Recent Advances in the Synthesis and Applications of Isothiocyanates[J]. Chinese Journal of Organic Chemistry, 2025, 45(7): 2350-2366.

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图/表 53

Scheme 1. General synthetic pathways for the synthesis of ITCs

Scheme 2. ITCs synthesis from CS2 and amine in the presence of DMAP

Scheme 3. DMT/NMM/TsO－ as desulfurized agent for ITCs synthesis

Scheme 4. Synthesis of ITCs from R-NH2 and CS2 in the presence of DMAP or DABCO as a catalyst

Scheme 5. Copper catalyzed synthesis of ITCs

Scheme 6. ITCs synthesis from S8 in the presence of TMSCF3 and AgSCF3

Scheme 7. Synthesis of ITCs from RNH2 and CS2 using triphosgene as a dehydrosulfurizing agent

Scheme 8. (Me)4NSCF3, a solid sulfurizing reagent for the synthesis of ITCs

Buffer	Initial pH	Final pH	Yield/%
Buffer	Initial pH	Final pH	1a	1b
K₂HPO₄＋KH₂PO₄ (1 mol/L)	6	6.45	Trace	91
	7	7.44	5	88
	8	8.84	15	77
	9	9.45	65	22
	10	10.18	82	8

Table 1. Reaction of dithiocarbamate triethylammonium salt with methyl acrylate in aqueous buffer at different pH

Scheme 9. ITCs synthesis from amine using CBr4

Scheme 10. Synthesis of ITCs using DIB from amines

Scheme 11. (a) Reaction pathways toward the synthesis of ITCs involving S8 with isocyanide and (b) nucleophilic activation of S8

Scheme 12. Se and Te catalyzed the transformation of isocyanides to ITCs

Scheme 13. Molybdenum catalyzed the transformation of isocyanides to ITCs

Scheme 14. Molybdenum catalyzed the transformation of isocyanides to ITCs

Scheme 15. Rhodium catalyzed the transformation of isocyanides to ITCs using S8

Scheme 16. Mechanism of nucleophilic activation of S8

Scheme 17. Proposed mechanistic pathways for the synthesis of thioureas from isocyanides and amines

Scheme 18. Synthesis of ITCs using tertiary amine as a base

Scheme 19. Lawesson’s reagent catalyzed synthesis of ITCs from isocyanides

Scheme 20. Staudinger-aza-Witting reaction for the synthesis of gluco-ITCs

Scheme 21. Synthesis of N-protected amino alkyl-NCS from N-protected amino alkyl-N3

Scheme 22. Synthesis of ITCs using Lawesson’s reagent under microwave irradiation

Scheme 23. Synthesis of ITC from hydroximoyl chloride and thiourea

Figure 1. Synthetic applications of isothiocyanates

Scheme 24. Metal-free synthesis of 2-aminobenzothiazoles

Scheme 25. DBU-mediated synthesis of Z-selective heterocycles

Scheme 26. Silica gel promoted synthesis of 2-aminothiazoli- dines

Scheme 27. Synthesis of thiazolidine-2-imine via cascade alkynylation/hydrothiolation

Scheme 28. Synthesis of 2-iminothiazolidines via telescoping reaction

Scheme 29. AlCl3-catalyzed annulation of DA cyclopropanes with ITCs

Scheme 30. Metal-free synthesis of 5-amino-1,2,4-thiadiazoles

Scheme 31. Cu-catalyzed synthesis of benzosultams

Scheme 32. BF3•OEt2-catalyzed denitrogenative transannulation

Scheme 33. Denitrogenative transannulation of 1-mesyl-1,2,3- triazoles

Scheme 34. Enantioselective synthesis of pyrrolidine based heterocyles

Scheme 35. Synthesis of functionalized tetrahydroquinazolines from o-haloanilines

Scheme 36. TfOH-promoted cascade trifluromethylation/cycli- sation

Scheme 37. Ring expansion of epoxy-sulfonamides with isothiocyanates

Scheme 38. [3＋2] umpolung annulations between 1,2,3-thia- diazoles and isothiocyanates

Scheme 39. Synthesis of thio-substituted phenanthridines from 2-biaryl isothiocyanates

Scheme 40. DABCO-catalyzed synthesis of 2-iminonaphtho- 1,3-oxathioles

Figure 2. Representation of electrophilic and nucleophilic center of ITCs

Scheme 41. Stereoselective synthesis of thioamides from ITCs and organolithium

Scheme 42. Use of ITCs as electrophile for electrophilic reaction of diazole

Scheme 43. Partial reduction of ITCs to thioformamides

Scheme 44. Synthesis of thiocarbamates and thiourea from ITCs

Scheme 45. Synthesis of unsymmetrical thiourea from ITCs at room temperature

Scheme 46. Trisubstituted unsymmetrical thiourea synthesis from ITCs

Scheme 47. Synthesis of unsymmetrical thiourea

Scheme 48. Synthesis of hydrazinecarbothioamides

Scheme 49. Synthesis of thiourea from ITCs

Scheme 50. Thioformamide synthesis followed by N-difluoromethyl amide synthesis

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