α-重氮锍盐作为自由基与多元活性物种前体的研究进展

doi:10.6023/cjoc202512047

摘要/Abstract

α-重氮锍盐是一类近年来发展迅速的新型重氮试剂. 在光照以及金属催化体系下, 该类化合物可作为α-重氮甲基自由基、卡拜自由基、叶立德自由基、卡宾、电子给体-受体(EDA)复合物及双阳离子等活性中间体前体, 相关反应已取得较为系统且深入的进展. 重点综述了近年来基于α-重氮锍盐的各类活性中间体的生成机制、参与的有机合成反应类型及相应的反应机理, 并对该领域的发展现状与面临的挑战进行了总结与展望.

关键词: α-重氮锍盐, 新型重氮试剂, 自由基, 活性中间体

α-Diazo sulfonium salts are a class of novel diazo reagents that have undergone rapid development in recent years. Under photoirradiation or metal-catalyzed systems, systematic and in-depth research progress has been achieved regarding the reactions of these compounds as precursors to various reactive intermediates, including α-diazomethyl radicals, carbyne radicals, ylide radicals, carbenes, electron donor-acceptor (EDA) complexes, and dicationic species. This review focuses on reviewing the generation mechanisms of various reactive intermediates based on α-diazo sulfonium salts, the types of organic synthesis reactions they participate in, and the corresponding reaction mechanisms. Finally, a summary and outlook are presented on the current development status and existing challenges in this field.

Key words: α-diazo sulfonium salts, novel diazo reagents, radicals, reactive intermediates

引用此文

李兴, 张自强, 林志远, 姚家成, 李鑫艳, 李强强, 宣俊. α-重氮锍盐作为自由基与多元活性物种前体的研究进展[J]. 有机化学, 2026, 46(4): 1376-1389.

Xing Li, Ziqiang Zhang, Zhiyuan Lin, Jiacheng Yao, Xinyan Li, Qiangqiang Li, Jun Xuan. Research Progress of α-Diazo Sulfonium Salts as Free Radicals and Multivariate Reactive Species Precursors[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1376-1389.

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图/表 18

图式1. 由高价碘化合物制备α-重氮锍盐

Scheme 1. Preparation of α-diazo sulfonium salt from hypervalent iodine compounds

图式2. 利用Tf2O制备α-重氮锍盐

Scheme 2. Preparation of α-diazo sulfonium salt with Tf2O

图式3. 光氧化还原催化α-重氮锍盐合成三唑

Scheme 3. Photoredox-catalyzed synthesis of triazoles from α-diazo sulfonium triflates

图式5. 光氧化还原催化三氟甲磺酸α-重氮锍盐合成α,α-二芳基羰基化合物

Scheme 5. Photoredox-catalyzed synthesis of α,α-diarylcycloalkenone compounds from α-diazo sulfonium triflates

图式4. 光氧化还原催化三氟甲磺酸α-重氮锍盐合成噁二唑和吡唑

Scheme 4. Photoredox-catalyzed synthesis of oxadiazole and pyrazole from α-diazo sulfonium triflates

图式6. 光氧化还原催化三氟甲磺酸α-重氮锍盐合成硫代氨基甲酸酯和氨基甲酸酯

Scheme 6. Photoredox-catalyzed synthesis of bis-dithiocarbamates and carbamates from α-diazo sulfonium triflates

图式7. 光氧化还原催化α-重氮锍盐修饰蛋白质

Scheme 7. Photoredox-catalyzed modification of proteins with α-diazo sulfonium salt

图式8. 光氧化还原催化三氟甲磺酸α-重氮锍盐通过形成卡拜自由基合成1,4-二羰基Z-烯烃

Scheme 8. Photoredox-catalyzed synthesis of 1,4-dicarbonyl Z-alkenes from α-diazonium sulfonium trifluoromethanesulfonates via carbyne radical formation

图式9. 光氧化还原催化α-重氮二氟乙基硫盐合成3-二氟甲基吡唑

Scheme 9. Photoredox-catalyzed synthesis of 3-difluoromethyl- pyrazole from α-diazodifluoroethyl sulfonium salt

图式10. 光氧化还原催化α-重氮二氟乙基硫盐合成三唑

Scheme 10. Photoredox-catalyzed synthesis of triazole from α-diazodifluoroethyl sulfonium salt

图式11. 光氧化还原催化三氟甲磺酸α-重氮锍盐合成噁二唑

Scheme 11. Photoredox-catalyzed synthesis of oxadiazole from α-diazo sulfonium

图式12. Rh催化三氟甲磺酸α-重氮锍盐和喹啉合成咪唑并喹啉

Scheme 12. Rh-catalyzed synthesis of imidazo[1,5-a]quinoline from α-diazo sulfonium triflates and quinoline

图式13. Rh催化三氟甲磺酸α-重氮锍盐和茚合成萘

Scheme 13. Rh-catalyzed synthesis of naphthalene from α-diazo sulfonium triflates and indene

图式14. Rh催化三氟甲磺酸α-重氮锍盐和吲哚合成喹啉

Scheme 14. Rh-catalyzed synthesis of quinoline from α-diazo sulfonium triflates and indole

图式15. Rh催化α-重氮锍盐的C—H/N—H官能团化

Scheme 15. Rh-catalyzed C—H/N—H functionalization of α-diazo sulfonium

图式16. 光氧化还原催化三氟甲磺酸α-重氮锍盐合成菲啶

Scheme 16. Photoredox-catalyzed synthesis of phenanthridine from α-diazo sulfonium triflates

图式17. 三氟甲磺酸α-重氮锍盐和α-乙烯苯胺合成喹啉

Scheme 17. Synthesis of quinoline from α-diazo sulfonium triflates and α-ethylaniline

图式18. 胺类化合物和三氟甲磺酸α-重氮锍盐合成甘胺酸衍生物

Scheme 18. Synthesis of glycine derivatives from amine compounds and α-diazo sulfonate triflates

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