Dowd-Beckwith Reaction: From Halogen Atom Transfer to Modern Initiation Strategies

doi:10.6023/cjoc202512032

Abstract

The Dowd-Beckwith reaction is an important strategy for constructing medium-sized rings and functionalized carbocyclic skeletons. With the advancement of radical chemistry, strategies such as transition metal catalysis, photoredox catalysis, and electrochemical catalysis have been applied to the Dowd-Beckwith reaction, which not only enriches the methods for radical generation but also significantly expands the reaction scope. This review summarizes the historical evolution and recent advances of the Dowd-Beckwith reaction, classified by the methods for generating key radicals, including halogen atom transfer (XAT), single electron transfer (SET), addition to unsaturated bonds, hydrogen atom transfer (HAT), and energy transfer (EnT).

Key words: radical, rearrangement, Dowd-Beckwith reaction, medium-sized ring

Cite this article

Mingqiang Li, Lei Zhou. Dowd-Beckwith Reaction: From Halogen Atom Transfer to Modern Initiation Strategies[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1428-1439.

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Fig. & Tab. 22

Scheme 1. Dowd-Beckwith reaction

Scheme 2. XAT process initiated by organotin reagents

Scheme 3. XAT process initiated by organosilicon reagents

Scheme 4. Dowd-Beckwith reaction involving aryl diazonium salts

Scheme 5. UV light-induced Dowd-Beckwith reaction

Scheme 6. Visible light-induced SET Dowd-Beckwith reaction

Scheme 7. Light-palladium synergistically induced Dowd- Beckwith reaction

Scheme 8. Carbon radical-mediated α-haloalkyl cycloketone ring-opening/amidation or esterification reaction

Scheme 9. Light/cobalt cooperative catalysis for dehydrogenative aromatization synthesis of arylamines

Scheme 10. Dowd-Beckwith/radical-polar crossover reaction

Scheme 11. Photoinduced decarboxylative Dowd-Beckwith reaction

Scheme 12. Regioselective ring cleavage of α-carboxymethyl-β-keto ester

Scheme 13. Photoredox-mediated carbonyl/imine transfer for olefin functionalization

Scheme 14. 1,3-Trifluoromethyl/alkynylation of α-vinyl-β-keto ester

Scheme 15. Photocatalytic expansion/acylation of cycloketone scaffolds

Scheme 16. Iron-catalyzed ring expansion/contraction reactions of β-keto ester

Scheme 17. Synthesis of the fused tricyclic skeleton in the total synthesis of Crinipellins

Scheme 18. Ring-expansion and cyclization reactions of alkynes

Scheme 19. Synthesis of lactams using Dowd-Beckwith reaction

Scheme 20. Ring-expansion reaction starting from C(sp3)—H bonds

Scheme 21. Skeleton rearrangement and C(sp3)—H alkylation

Scheme 22. Energy transfer-initiated Dowd-Beckwith ring expansion reaction

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Dowd-Beckwith反应: 从卤原子转移到现代引发策略