Recent Progress in Sulfonyl Derivative Mediated Radical Aryl Migration

doi:10.6023/cjoc202601018

Abstract

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

Cite this article

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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Fig. & Tab. 47

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

Scheme 2. Synthetic pathways of several sulfonamide derivatives

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

Scheme 4. Sulfonylarylation of N-sulfonyl α-methacrylamide

Scheme 5. Chiral sulfoxide mediated asymmetric aryl migration reaction

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

Scheme 7. Smiles rearrangement reaction of benzenesulfonyl propionylamide

Scheme 8. Smiles rearrangement initiated by carbonylalkynamide coupling

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

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

Scheme 11. Energy transfer-mediated Smiles rearrangement of sulfonamides

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

Scheme 13. Photoelectrochemical rearrangement of cyclic tertiary alcohol

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

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

Scheme 16. Enzyme-catalyzed asymmetric Smiles rearrangement reactions

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

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

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

Scheme 20. Reactions involving sulfone difunctionalization reagents

Scheme 21. Bifunctional reagents mediated synthesis of heterocyclic compounds

Scheme 22. Difunctionalization of ethene via functional group migration strategy

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

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

Scheme 25. Electron-rich olefins participate in bifunctional reactions

Scheme 26. Intermolecular aminoarylation of activated olefins with sulfonamide

Scheme 27. Intramolecular difunctionalization of unactivated alkene based sulfonamide

Scheme 28. Difunctionalization of alkenes with sulfinamide as bifunctional reagent

Scheme 29. Chiral arylsulfonyl amides mediated aminylaromatication of olefins

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

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

Scheme 32. Isomenthol backbone-mediated aryl migration reactions

Scheme 33. Smiles rearrangement of distal olefin sulfonates

Scheme 34. Sulfonylarylation of alkyne propyl sulfonate

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

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

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

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

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

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

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

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

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

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

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

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

Scheme 47. Comparison of aryl migration of different sulfonate derivatives

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