自由基硒磺酰化研究进展

doi:10.6023/cjoc202510020

摘要/Abstract

硒磺酰化已成为同时构建C—Se和C—S键最为快速和实用的方法之一, 该转化制备的硒代砜类化合物不仅在药物研发、天然产物结构单元修饰及功能材料中占据重要地位, 而且能作为通用的合成中间体实现进一步转化. 自由基硒磺酰化具有反应活性高、条件温和及官能团耐受性优良等特点, 近二十年来取得了蓬勃发展. 从磺酰化试剂的种类出发, 将该领域细分为来源于硒磺酸酯、磺酰肼、亚磺酸钠/亚磺酸、芳基重氮盐与1,4-二氮杂双环[2.2.2]辛烷-1,4-二鎓-1,4-二亚磺酸(DABSO)结合、环丁酮肟酯与DABSO结合以及炔烃与DABSO结合, 简要论述了近年来自由基硒磺酰化反应的研究进展.

关键词: 自由基反应, 硒磺酰化, 磺酰化试剂, 硒代砜

Selenosulfonylation has emerged as one of the most efficient and practical methods for the simultaneous construction of C—Se and C—S bonds. The selenosulfone compounds prepared by this transformation not only play significant roles in drug development, natural product structural modification, and functional materials, but also serve as versatile synthetic intermediates for further transformations. Over the past two decades, radical selenosulfonylation has experienced considerable progress, characterized by its high reactivity, mild reaction conditions, and excellent functional group tolerance. The recent advances in radical selenosulfonation systematically categorized based on the types of sulfonylation reagents employed, including those derived from selenosulfonate salt, sulfonylhydrazine, sodium sulfite or sulfinic acid, aryl diazonium salt combined with 1,4-diazabicyclo[2.2.2]octane-1,4-diium-1,4-disulfinate (DABSO), cyclobutanone oxime ester combined with DABSO, and alkyne combined with DABSO. A concise overview of the recent developments in this field is provided accordingly.

Key words: radical reaction, selenosulfonylation, sulfonylation reagent, selenosulfone

引用此文

刘世峥, 窦明煜, 崔玉, 窦建民, 魏文廷. 自由基硒磺酰化研究进展[J]. 有机化学, 2026, 46(4): 1621-1634.

Shizheng Liu, Mingyu Dou, Yu Cui, Jianmin Dou, Wenting Wei. Research Progress on Radical Selenosulfonylation[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1621-1634.

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图/表 27

图1. 磺酰化试剂概述

Figure 1. Overview of sulfonylation reagents

图式1. 硒磺酸酯裂解路径示意图

Scheme 1. Schematic diagram of the selenyl sulfonate cracking pathway

图式2. 烯烃与硒磺酸酯的自由基硒磺酰化

Scheme 2. Radical selenosulfonylation of olefins with selenosulfonate salts

图式3. 烯烃同一位点的硒磺酰化

Scheme 3. Selenosulfonylation at the same site of olefins

图式4. 烯基叠氮的硒磺酰化

Scheme 4. Selenosulfonylation of vinyl azides

图式5. 乙烯基重氮的1,3-硒磺酰化

Scheme 5. 1,3-Selenosulfonylation of ethylene diazoniums

图式6. 丁烯基苯并噻唑砜的硒磺酰化

Scheme 6. Selenosulfonylation of butenyl benzothiazole sulfones

图式7. 炔烃与硒磺酸酯的自由基硒磺酰化

Scheme 7. Radical selenosulfonylation of alkynes with selenosulfonate salts

图式8. 炔胺的硒磺酰化

Scheme 8. Selenosulfonylation of ynamides

图式9. 乙炔的1,2-硒磺酰化

Scheme 9. 1,2-Selenosulfonylation of acetylene

图式10. 炔基重氮化物的1,3-硒磺酰化

Scheme 10. 1,3-Selenosulfonylation of alkynyl diazo compounds

图式11. 1,6-烯炔的自由基硒磺酰化

Scheme 11. Radical selenosulfonylation of 1,6-enynes

图式12. 1,3-烯炔的1,4-硒磺酰化

Scheme 12. 1,4-Selenosulfonylation of 1,3-enynes

图式13. BCP的自由基硒磺酰化

Scheme 13. Radical selenosulfonylation of BCP

图式14. 2,2,2-三氟重氮乙烷的自由基硒磺化

Scheme 14. Radical selenosulfonylation of 2,2,2-trifluorodiazo- ethane

图式15. 马来酰亚胺的硒磺酰化

Scheme 15. Selenosulfonylation of maleimides

图式16. 磺酰肼作为硒磺酰化试剂与炔烃反应

Scheme 16. Reaction of sulfonylhydrazines as selenosulfonylation reagent with alkynes

图式17. 亚磺酸钠作为硒磺酰化试剂与炔烃反应

Scheme 17. Sodium arenesulfinates as selenosulfonylation reagent react with alkynes

图式18. 亚磺酸作为硒磺酰化试剂与烯炔反应

Scheme 18. Reaction of sulfinic acids as selenosulfonylation reagent with enynes

图式19. 未活化烯烃的四组分1,2-硒磺酰化

Scheme 19. Four component 1,2-selenosulfonylation of unactivated olefins

图式20. 炔烃的四组分硒磺酰化

Scheme 20. Four component selenosulfonylation of alkynes

图式21. 烯炔的四组分硒磺酰化

Scheme 21. Four component selenosulfonylation of enynes

图式22. 丙二烯的1,2-硒磺酰化

Scheme 22. 1,2-Selenosulfonylation of allenes

图式23. 使用环丁酮肟酯的炔烃硒磺酰化

Scheme 23. Selenosulfonylation of alkynes using cycloketone oxime esters

图式24. 使用环丁酮肟酯的1,6-烯炔硒磺酰化

Scheme 24. Selenosulfonylation of 1,6-enynes using cycloketone oxime esters

图式25. 使用环丁酮肟酯的1,3-烯炔硒磺酰化

Scheme 25. Selenosulfonylation of 1,3-enynes using cycloketone oxime esters

图式26. 炔烃与DABSO结合作为磺酰化试剂

Scheme 26. Alkynes combine with DABSO as sulfonylation reagents

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