双功能二氧化硫替代物在合成磺酰类化合物中的研究进展

doi:10.6023/cjoc202305014

摘要/Abstract

近年来通过二氧化硫插入合成磺酰类化合物的合成方法受到了研究者的关注. 多种二氧化硫替代物参与的磺酰化反应被相继报道, 并成功用于多种磺酰类化合物如砜、磺酰氟和磺酰胺等的合成. 其中部分二氧化硫替代物展现出了双功能的作用——既作为二氧化硫源用于构建磺酰基, 又作为体系中的还原剂. 具有还原性的二氧化硫阴离子自由基在这些反应中起到了关键作用, 提高了磺酰化反应的效率和原子经济性. 重点介绍了近年来这类双功能二氧化硫替代物在磺酰类化合物合成中的研究进展.

关键词: SO₂插入, SO₂阴离子自由基, 双功能试剂, 磺酰化

The synthesis of sulfonyl compounds via sulfur dioxide insertion has received considerable attention from chemists recently. Various sulfonyl compounds such as sulfones, sulfonyl fluorides and sulfonamides have been prepared through the fixation of sulfur dioxide by employing sulfur dioxide surrogates. In particular, some of sulfur dioxide surrogates display a bifunctional role: not only serving as a source of sulfur dioxide, but also acting as a reducing agent in the desired sulfonylation reactions. The reductive sulfur dioxide anion radical plays a key role in these transformations, and the efficiency and atomic economy of these reactions have been enhanced greatly. This review highlights the recent advances of such bifunctional sulfur dioxide surrogates involved sulfonylation transformations.

Key words: SO₂ insertion, SO₂ anion radical, bifunctional reagent, sulfonylation

引用此文

吴宇恒, 颜岩, 寮渭巍. 双功能二氧化硫替代物在合成磺酰类化合物中的研究进展[J]. 有机化学, 2023, 43(11): 3713-3727.

Yuheng Wu, Yan Yan, Weiwei Liao. Recent Advances of Bifunctional Sulfur Dioxide Surrogates in Synthesis of Sulfonyl Compounds[J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3713-3727.

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图/表 26

图1. 具有生物活性的磺酰类化合物

Figure 1. Biologically relevant sulfonyl compounds

图式1. 双功能二氧化硫替代物

Scheme 1. Bifunctional sulfur dioxide substitutes

图式2. 碘代芳烃合成芳基砜和芳基磺酰胺

Scheme 2. Synthesis of aryl sulfones and aryl sulfonamides from idoarenes

图式3. 连二亚硫酸钠通过脱羧磺酰化构建烷基砜

Scheme 3. Sodium dithionite to construct alkyl sulfones by decarboxylation sulfonylation

图式 4. 连二亚硫酸钠氧化还原活性酯与烯、炔烃的多组分偶联

Scheme 4. Multicomponent coupling of sodium dithionite, NHP esters and olefins

图式5. 氧化还原活性酯脱羧-磺酰化生成磺酰氟

Scheme 5. Synthesis of sulfonyl fluoride by decarboxylation- sulfonylation of NHP ester

图式6. ${{\text{S}}_{2}}\text{O}_{4}^{2}$和${{\text{S}}_{2}}\text{O}_{5}^{2}$结构示意

Scheme 6. Schematic diagram of the structures of ${{\text{S}}_{2}}\text{O}_{4}^{2}$ and ${{\text{S}}_{2}}\text{O}_{5}^{2}$

图式7. 三组分偶联反应合成2-磺酰喹啉

Scheme 7. Synthesis of 2-sulfonylquinolines by three-compo- nent coupling reaction

图式8. TFA促进的多组分偶联合成硫代磺酸酯

Scheme 8. TFA-promoted multicomponent coupling reaction for synthesis of thiosulfonates

图式9. 由芳基重氮盐合成芳基磺酰氟

Scheme 9. Synthesis of arylsulfonyl fluorides from aryldiazonium salts

图式10. 二氧化硫插入/1,5-HAT串联反应合成烯基砜

Scheme 10. SO2 insertion/1,5-HAT tandem reaction to synthesize alkenyl sulfones

图式11. 由芳基重氮盐合成2-磺酰基乙腈

Scheme 11. Synthesis of 2-sulfonylacetonitrile from aryldiazonium salts

图式12. 四组分偶联合成芳基砜

Scheme 12. Four-component coupling reaction for the synthesis of aryl sulfones

图式13. 焦亚硫酸钠参与的硝基芳烃和硼酸的直接磺胺化反应

Scheme 13. Direct sulfonation of nitroaromatic hydrocarbons and boric acids by metabisulfites

图式14. SO2/I交换的策略构建二芳基环砜

Scheme 14. Construction of diaryl sulfones via SO2/I exchange

图式15. Na2S2O5参与的多组分反应合成氟烷基取代的磺酰亚胺衍生物

Scheme 15. Multicomponent cyclization with an inorganic sulfur dioxide surrogate: straightforward construction of difluorinated benzosultams

图式16. Rongalite试剂合成磺酰胺磺酰氟及不对成砜

Scheme 16. Synthesis of sulfonamides, sulfonyl fluorides and asymmetric sulfones by Rongalite reagent

图式17. Rongalite试剂与二芳基碘鎓盐合成磺酰胺

Scheme 17. Synthesis of sulfonamides with Rongalite reagent and diaryliodonium salt

图式18. 由Rongalite试剂合成N-氨基磺酰胺

Scheme 18. Synthesis of N-sulfamides by rongalite

图式19. 由Rongalite试剂合成N-杂芳基砜和硫醚衍生物

Scheme 19. Synthesis of N-heterocyclic sulfones and sulfides from Rongalite reagents

图式20. 亚氨基自由基与烯烃的串联环化反应

Scheme 20. Tandem cyclization of imino radicals with alkenes

图式21. Rongalite试剂作为亚甲基及磺酰基来源

Scheme 21. Rongalite reagent as a source of methylene and sulfonyl group

图式22. 二氧化硫脲作为磺酰基来源

Scheme 22. Thiourea dioxide as a sulfonyl source

图式23. 光催化下二氧化硫脲对烯烃的磺酰化

Scheme 23. Photocatalytic sulfonylation of olefins with thiourea dioxide

图式24. 二氧化硫脲的还原插砜反应

Scheme 24. Reductive sulfonylation of thiourea dioxide

图式25. 卤代烃二氧化硫脲偶联生成磺酸

Scheme 25. Coupling of halogenated hydrocarbon with dioxide thiourea for sulfonic acid

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