Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications

doi:10.6023/cjoc202401035

Abstract

Following the rapid advance of radical chemistry, a range of halogen atom transfer (XAT) reagents have been developed by chemists for alkyl and aryl halides, which typically feature strong bond strengths and high redox potentials. These reagents facilitate the extraction of halogen atoms from alkyl and aryl moieties via radical substitution pathways, thus generating radical species that undergo subsequent chemical transformations for the synthesis of valuable molecules. The unique reactivity and versatility of these XAT reagents have attracted much attention in organic synthesis. Recent reviews of XAT reagents have mainly focused on elucidating reaction mechanisms and classifying different types with limited exploration of activation strategies. In light of this, this paper provides a summary of the activation strategies for XAT reagents over the past three years. The discussion is organized into four aspects based on different strategies, namely single electron transfer, hydrogen atom transfer, energy transfer, and electron donor-acceptor (EDA) complexes. This review aims to address the research gaps in activation strategies of XAT reagents, providing new theoretical support and perspectives for the field.

Key words: halogen atom transfer, single electron transfer, hydrogen atom transfer, energy transfer, electron donor-acceptor (EDA) complex

Cite this article

Yifeng Jiang, Yanli Yin, Zhiyong Jiang. Recent Advances in Strategies for Halide Atom Transfer (XAT) and Their Applications[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1733-1759.

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Fig. & Tab. 45

Scheme 1. Bond dissociation energy and redox potential

Scheme 2. Activation modes for halogen atom transfer

Scheme 3. Construction of gem-difluoroalkenes through free radical addition

Scheme 4. Dehalogenated alkylation through radical addition

Scheme 5. Synthesis of alanine analogues via Giese reaction

Scheme 6. Access to α-arylation of cyclic ketones through radical addition to enamine intermediates

Scheme 7. Synthesis of sterically hindered amines via radical addition

Scheme 8. Construction of polycyclic benzazepine derivatives via intermolecular radical cyclization

Scheme 9. Construction of C-glycosylated phenanthridines via radical addition and cyclization

Scheme 10. Stereodivergent synthesis of α-iodoboronic esters

Scheme 11. Diarylation of alkenes via radical addition and coupling

Scheme 12. Photoinduced radical cross-coupling

Scheme 13. Acyldifluoroalkylation of alkenes through cooperative NHC and organic photocatalysts

Scheme 14. Visible light-mediated C(sp3)—C(sp2) cross coupling via synergistic halogen-atom transfer and nickel catalysis

Scheme 15. Cobalt-catalyzed allylic fluoroalkylation of terpenes

Scheme 16. Catalytic defluorinative ketyl-olefin coupling by halogen-atom transfer

Scheme 17. Three-component coupling of aryl halides, olefins, and O2

Scheme 18. Trifluoropropanation of organic halides

Scheme 19. Synthesis of C-alkyl glycosides via Smile rearrangement

Scheme 20. Silyl-mediated photoredox-catalyzed radical-radical cross-coupling reaction of alkyl bromides with ketoesters

Scheme 21. Access to trifluoromethyl ketones through radical-radical cross-coupling

Scheme 22. Biomimetic SH2 cross-coupling mechanism for constructing quaternary carbon

Scheme 23. Synthesis of β-chiral sulfones through radical-radical cross-coupling

Scheme 24. Difluoromethylation of unactivated alkenes

Scheme 25. Photoinduced halogen-atom transfer mediated by N-heterocyclic carbene-ligated boryl radicals

Scheme 26. 1,2-Aminoxyalation of olefins

Scheme 27. Cross coupling reaction via cooperative photoredox and copper catalysis

Scheme 28. Copper-mediated cross-coupling reactions

Scheme 29. Construction of quaternary carbons via halogen atom transfer enabled by reductive activation

Scheme 30. Photoredox catalytic chlorination of quinoxolone

Scheme 31. Photoinduced decarboxylative chlorination media- ted by halogen atom transfer

Scheme 32. Photo-alkylation/-arylation of ortho-diketones

Scheme 33. Photoredox and Nickel-mediated C(sp3)-C(sp2) cross coupling

Scheme 34. Copper-catalyzed amination of alkyl iodides

Scheme 35. Copper-catalyzed three-component reactions

Scheme 36. Nickel-catalyzed cross coupling of electrophiles

Scheme 37. Cooperative photoredox and nickel catalysis to construct aminoformamides

Scheme 38. Photoinduced manganese-catalyzed functionalization of alkene hydrofluoroalkyl groups

Scheme 39. Paired electrolysis-enabled nickel-catalyzed enantioselective reductive cross-coupling between α-chloroesters and aryl bromides

Scheme 40. Halogen-atom transfer reaction enabled by hydrogen tunneling

Scheme 41. Coupling reactions enabled by halogen atom transfer and energy transfer

Scheme 42. Three-component SH2 reaction

Scheme 43. Visible light-induced phosphine-catalyzed 1,3-carbobromination of allyl carboxylates

Scheme 44. Visible light-induced defluorinative allylation of difluoromethyl ketones

Scheme 45. EDA-mediated synthesis of γ-lactam or allyl difluoride derivatives

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卤素原子转移(XAT)策略及应用新进展