磺酰基衍生物介导的自由基型芳基迁移反应进展

doi:10.6023/cjoc202601018

摘要/Abstract

磺酰基衍生物介导的自由基型芳基迁移反应, 是实现官能团迁移、分子骨架重排以及取代芳香类化合物高效构建的关键策略, 在复杂分子精准合成领域具有重要应用价值. 依据磺酰基衍生物的结构类型, 系统总结了近年来由磺酰胺类、芳基砜衍生物、磺酸酯类及其他磺酰基衍生物介导的芳(杂)基迁移反应的最新研究进展, 重点评述了各类反应的设计思路与机理研究, 并对该领域的未来发展方向进行了展望.

关键词: 磺酰基衍生物, 芳基迁移, 自由基, 芳(杂)环, 串联反应

Sulfonyl derivative-mediated radical-type aryl migration reactions represent a pivotal strategy for achieving functional group migration, molecular skeleton rearrangement, and the efficient construction of substituted aromatic compounds, and they hold significant application value in the field of precision synthesis of complex molecules. Classified by the structural types of sulfonyl derivatives, this review systematically summarizes the latest research progress in aryl (hetero)aryl migration reactions mediated by sulfonamides, aryl sulfone derivatives, sulfonic acid esters, and other sulfonyl compounds in recent years. It focuses particularly on discussing the design concepts and mechanistic investigations of various reactions, and also provides an outlook on the future development directions of this field.

Key words: sulfonyl derivative, aryl migration, radical, (hetero)aromatic rings, cascade reaction

引用此文

许俊华, 张珂瑗, 贺重隆, 段新华, 刘乐. 磺酰基衍生物介导的自由基型芳基迁移反应进展[J]. 有机化学, 2026, 46(4): 1255-1283.

Junhua Xu, Keyuan Zhang, Chonglong He, Xin-Hua Duan, Le Liu. Recent Progress in Sulfonyl Derivative Mediated Radical Aryl Migration[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1255-1283.

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图/表 47

图式1. 离子型与自由基型芳基迁移反应比较

Scheme 1. Comparison of ion-type and free radical-type aryl migration reaction

图式2. 几种磺酰基衍生物的合成路径

Scheme 2. Synthetic pathways of several sulfonamide derivatives

图式3. 基于N-磺酰基α-甲基丙烯酰胺骨架的芳基迁移反应

Scheme 3. Aryl migration reactions based on N-sulfonyl α-methylacrylamide backbone

图式4. N-磺酰基α-甲基丙烯酰胺的砜芳基化反应

Scheme 4. Sulfonylarylation of N-sulfonyl α-methacrylamide

图式5. 手性亚砜介导的不对称芳基迁移反应

Scheme 5. Chiral sulfoxide mediated asymmetric aryl migration reaction

图式6. D-叔亮氨酸作为手性助剂介导的选择性芳基迁移

Scheme 6. D-Tertiary leucine as a chiral auxiliary for selective aryl migration

图式7. 苯磺酰基丙炔酰胺的Smiles重排反应

Scheme 7. Smiles rearrangement reaction of benzenesulfonyl propionylamide

图式8. 羰基炔酰胺偶联引发的Smiles重排反应

Scheme 8. Smiles rearrangement initiated by carbonylalkynamide coupling

图式9. 远端烯基取代N-磺酰基炔胺的自由基串联环化反应

Scheme 9. Radical tandem cyclization reaction of distal alkene substituted N-sulfonylalkylamine

图式10. C—X键活化实现的分子内芳基迁移

Scheme 10. Intramolecular aryl migration achieved by C—X bond activation

图式11. 能量转移介导的磺酰胺类化合物的Smiles重排反应

Scheme 11. Energy transfer-mediated Smiles rearrangement of sulfonamides

图式12. 3-磺酰氨基环丁酮肟酯类化合物介导的芳基迁移

Scheme 12. 3-Sulfonylaminocyclobutanone oxime ester-mediated migration of aryl groups

图式13. 环烷醇的光电化学重排反应

Scheme 13. Photoelectrochemical rearrangement of cyclic tertiary alcohol

图式14. 2-溴-N-芳基-N-(芳磺酰基)酰胺的分子内级联反应

Scheme 14. Intramolecular cascade reaction of 2-bromo-N-aryl-N-(aromatasulfonyl)amide

图式15. 2-溴-N-(芳磺酰基)酰胺的分子内级联反应

Scheme 15. Intramolecular cascade reaction of 2-bromo-N- (aromaticsulfonyl)amide

图式16. 酶催化的不对称Smiles重排反应

Scheme 16. Enzyme-catalyzed asymmetric Smiles rearrangement reactions

图式17. 双功能试剂实现烯烃的“对接-迁移”反应策略

Scheme 17. Docking-migration reaction of olefins with bifunctional reagent

图式18. α-二氟溴代磺酰基试剂与烯烃的对接迁移反应

Scheme 18. Docking migration reaction between α-difluoro- bromated sulfonyl reagent and olefins

图式19. α-二烷基溴代磺酰基试剂与烯烃的对接迁移反应

Scheme 19. Docking and migration reaction of α-dialkylbromosulfonyl reagent with olefins

图式20. 砜类双官能团化试剂参与的反应

Scheme 20. Reactions involving sulfone difunctionalization reagents

图式21. 双官能团化试剂介导的杂环化合物的合成

Scheme 21. Bifunctional reagents mediated synthesis of heterocyclic compounds

图式22. 通过官能团迁移策略实现的乙烯的双官能团化反应

Scheme 22. Difunctionalization of ethene via functional group migration strategy

图式23. α-二烷基溴代磺酰基试剂与炔烃的对接迁移反应

Scheme 23. Docking-migration reaction of α-dialkyl bromosulfonyl reagents with alkyne

图式24. α-二烷基溴代磺酰基试剂与醛的对接迁移反应

Scheme 24. Docking migration reaction between α-dialkyl bromosulfonyl reagent and aldehyde

图式25. 富电子烯烃参与的双官能团化反应

Scheme 25. Electron-rich olefins participate in bifunctional reactions

图式26. 磺酰胺介导的活化烯烃的分子间氨基芳基化反应

Scheme 26. Intermolecular aminoarylation of activated olefins with sulfonamide

图式27. 未活化烯烃基于磺酰胺的分子内双官能团化反应

Scheme 27. Intramolecular difunctionalization of unactivated alkene based sulfonamide

图式28. 亚磺酰胺作为双官能化试剂介导的烯烃双官能团化

Scheme 28. Difunctionalization of alkenes with sulfinamide as bifunctional reagent

图式29. 手性芳基亚磺酰胺参与的烯烃氨基芳基化反应

Scheme 29. Chiral arylsulfonyl amides mediated aminylaromatication of olefins

图式30. 基于手性亚磺酰胺的分子内不对称远程芳基化反应

Scheme 30. Intramolecular asymmetric remote arylation reactions based on chiral sulfenamides

图式31. XAT策略引发的磺酸酯骨架的芳基迁移

Scheme 31. XAT strategy-induced aryl migration on sulfonate backbones

图式32. 异薄荷醇骨架介导的芳基迁移反应

Scheme 32. Isomenthol backbone-mediated aryl migration reactions

图式33. 远端烯烃磺酸酯的Smiles重排反应

Scheme 33. Smiles rearrangement of distal olefin sulfonates

图式34. 炔丙基磺酸酯的磺酰基芳化反应

Scheme 34. Sulfonylarylation of alkyne propyl sulfonate

图式35. 铱(III)催化邻炔基芳基乙烯基硅烷与芳基磺酰叠氮的环芳构化反应

Scheme 35. Iridium(III)-catalyzed cycloaromatization of o-alkyl aryl vinyl silanes with aryl sulfonyl azides

图式36. 芳基磺酰乙酸酯作为双官能团化试剂的炔烃双官能团化反应

Scheme 36. Alkyne bifunctionalization reaction of aryl sulfonylacetate as a difunctional reagent

图式37. 芳基磺酰乙酸酯作为双官能团化试剂的烯烃双官能团化反应

Scheme 37. Alkylene difunctionalization reaction of aryl sulfonylacetate as a difunctional reagent

图式38. 烷基杂芳基砜作为双官能团化试剂参与的烯烃双官能团化反应

Scheme 38. Alkyl heteroaryl sulfone as a bifunctionalization reagent in the bifunctionalization reaction of olefins

图式39. 可见光驱动的光氧化还原催化分子内级联反应

Scheme 39. Visible light-driven photoredox-catalyzed intramolecular cascades

图式40. 基于手性亚砜的分子内不对称远程芳基化反应

Scheme 40. Intramolecular asymmetric remote arylation reactions based on chiral sulfoxides

图式41. 双砜试剂作为双源供体的烯烃双官能团化反应

Scheme 41. Bifunctional reaction of olefin bifunctionalization of disulfone reagent as a bisource donor

图式42. 以丁烯基苯并噻唑砜骨架为原料的Smiles重排反应

Scheme 42. Smiles rearrangement reaction using butene benzothiazole sulfone skeleton as raw material

图式43. 以丁烯基苯并噻唑砜骨架为原料不释放SO2的Smiles重排反应

Scheme 43. Smiles rearrangement reaction without releasing SO2 using buteneylbenzothiazole sulfone backbone as raw material

图式44. 磺酰亚胺介导的未活化γC(sp3)—H键官能团化反应

Scheme 44. Sulfonimide-mediated functionalization of unactivated γC(sp3)—H bonds

图式45. α-羧基磺酰基试剂介导的脱羧-脱磺酰基双官能团化反应

Scheme 45. α-carboxysulfonyl reagent-mediated decarboxylation-desulfonyl bifunctionalization

图式46. 以磺酰基α-烯烃为单体的“无SO2”自由基均聚反应

Scheme 46. “SO2-free” radical homopolymerization reaction with sulfonyl α-olefins as monomers

图式47. 不同磺酰基衍生物的芳基迁移比较

Scheme 47. Comparison of aryl migration of different sulfonate derivatives

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