Dowd-Beckwith反应: 从卤原子转移到现代引发策略

doi:10.6023/cjoc202512032

摘要/Abstract

Dowd-Beckwith反应是构建中环及官能化碳环骨架的重要策略. 随着自由基化学的发展, 过渡金属催化、光氧化还原催化、电化学催化等策略也被应用于Dowd-Beckwith反应, 在丰富自由基引发方式的同时, 也拓展了反应的底物类型. 根据获得引发Dowd-Beckwith反应的关键自由基的方式, 从卤原子转移、单电子转移、不饱和键加成、氢原子转移和能量转移五个方面, 对该反应的历史沿革和最新进展做了总结.

关键词: 自由基, 重排, Dowd-Beckwith反应, 中环

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

引用此文

李明强, 周磊. Dowd-Beckwith反应: 从卤原子转移到现代引发策略[J]. 有机化学, 2026, 46(4): 1428-1439.

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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图/表 22

图式1. Dowd-Beckwith反应

Scheme 1. Dowd-Beckwith reaction

图式2. 有机锡试剂引发的XAT过程

Scheme 2. XAT process initiated by organotin reagents

图式3. 有机硅试剂引发的XAT过程

Scheme 3. XAT process initiated by organosilicon reagents

图式4. 芳基重氮盐参与的Dowd-Beckwith反应

Scheme 4. Dowd-Beckwith reaction involving aryl diazonium salts

图式5. 紫外光诱导的Dowd-Beckwith反应

Scheme 5. UV light-induced Dowd-Beckwith reaction

图式6. 可见光诱导SET的Dowd-Beckwith反应

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

图式7. 光钯协同诱导的Dowd-Beckwith反应

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

图式8. 碳自由基介导的α-卤代烷基环酮环张开/氨化或酯化反应

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

图式9. 光/钴协同催化脱氢芳构化合成芳胺

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

图式10. Dowd-Beckwith/自由基-极性交叉反应

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

图式11. 光诱导脱羧的Dowd-Beckwith反应

Scheme 11. Photoinduced decarboxylative Dowd-Beckwith reaction

图式12. α-羧甲基-β-酮酯的区域选择性环裂解

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

图式13. 光介导的羰基/亚胺基转移的烯烃官能化

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

图式14. α-乙烯基-β-酮酯的1,3-三氟甲基/炔基化

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

图式15. 光催化环酮的扩环/酰化骨架编辑

Scheme 15. Photocatalytic expansion/acylation of cycloketone scaffolds

图式16. 铁催化β-酮酸酯的扩环/缩环反应

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

图式17. Crinipellins全合成中稠合三环骨架的合成

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

图式18. 炔烃类的扩环-环化反应

Scheme 18. Ring-expansion and cyclization reactions of alkynes

图式19. 利用Dowd-Beckwith反应合成内酰胺

Scheme 19. Synthesis of lactams using Dowd-Beckwith reaction

图式20. C(sp3)—H键活化的环扩张反应

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

图式21. 骨架重排和C(sp3)—H烷基化

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

图式22. 能量转引发的Dowd-Beckwith扩环反应

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

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