卤素原子转移(XAT)策略及应用新进展

doi:10.6023/cjoc202401035

摘要/Abstract

随着自由基化学的发展, 对于具有较强键能且高氧化还原电位的烷基和芳基卤化物, 化学家们开发了一系列卤素原子转移(XAT)试剂. 这些试剂通过自由基取代途径攫取烷基和芳基的卤素原子, 并成功完成后续的官能团转化, 从而合成目标分子. 这些XAT试剂因其独特的反应性以及在有机合成中的多功能性而受到广泛关注. 近年来对于XAT试剂的综述主要集中于反应机理和种类的报道, 而对于其活化策略的研究较为有限. 基于此, 总结了近三年来关于XAT试剂的活化策略, 包括单电子转移、氢原子转移、能量转移和电子供体-受体(EDA)复合物四个方面进行阐述与讨论, 旨在弥补XAT试剂活化策略方面的研究空白, 为该领域提供新的理论支持和研究视角.

关键词: 卤素原子转移, 单电子转移, 氢原子转移, 能量转移, 电子供体-受体(EDA)复合物

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

引用此文

蒋译锋, 尹艳丽, 江智勇. 卤素原子转移(XAT)策略及应用新进展[J]. 有机化学, 2024, 44(6): 1733-1759.

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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图/表 45

图式1. 键解离能及氧化还原电势

Scheme 1. Bond dissociation energy and redox potential

图式2. 卤素原子转移试剂活化方式

Scheme 2. Activation modes for halogen atom transfer

图式3. 基于自由基加成构建偕二氟烯烃

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

图式4. 基于自由基加成脱卤烷基化

Scheme 4. Dehalogenated alkylation through radical addition

图式5. 通过Giese反应合成丙氨酸类似物

Scheme 5. Synthesis of alanine analogues via Giese reaction

图式6. 利用烯胺中间体通过自由基加成实现环状酮的α-芳基化

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

图式7. 自由基加成实现空间受阻胺的合成

Scheme 7. Synthesis of sterically hindered amines via radical addition

图式8. 分子内自由基环化合成多环苯并氮杂?衍生物

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

图式9. 自由基加成环化构建C-糖基化菲啶类化合物

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

图式10. α-碘硼酸酯的立体发散型合成

Scheme 10. Stereodivergent synthesis of α-iodoboronic esters

图式11. 自由基加成和偶联对烯烃实现双芳基化

Scheme 11. Diarylation of alkenes via radical addition and coupling

图式12. 光介导的自由基交叉偶联

Scheme 12. Photoinduced radical cross-coupling

图式13. 氮杂卡宾与有机光催化剂协同催化实现烯烃的酰化二氟烷基化

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

图式14. 光介导的卤素原子转移和镍协同催化实现C(sp3)—C(sp2)交叉偶联

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

图式15. 钴催化萜烯烃烷氟化反应

Scheme 15. Cobalt-catalyzed allylic fluoroalkylation of terpenes

图式16. 卤素原子转移的催化脱氟醛-烯烃偶联

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

图式17. 芳基卤化物、烯烃和氧气三组分偶联

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

图式18. 有机卤化物的三氟丙基化反应

Scheme 18. Trifluoropropanation of organic halides

图式19. 通过Smile-重排合成C-烷基糖苷

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

图式20. 硅介导光催化烷基溴化物和酮酯的自由基-自由基交叉偶联

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

图式21. 自由基交叉偶联合成三氟甲基酮类

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

图式22. 仿生SH2交叉偶联构建四级碳

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

图式23. 自由基交叉偶联合成β-手性砜

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

图式24. 未活化烯烃二氟甲基化

Scheme 24. Difluoromethylation of unactivated alkenes

图式25. N-杂环卡宾配位硼自由基介导的光诱导卤原子转移

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

图式26. 烯烃的1,2-胺氧烷基化反应

Scheme 26. 1,2-Aminoxyalation of olefins

图式27. 光敏剂与铜协同催化的交叉偶联反应

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

图式28. 金属铜介导的交叉偶联

Scheme 28. Copper-mediated cross-coupling reactions

图式29. 还原激活的卤素原子转移试剂介导构建四级碳

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

图式30. 光氧化还原催化喹喔啉酮氯化反应

Scheme 30. Photoredox catalytic chlorination of quinoxolone

图式31. 卤素原子转移介导的光诱导脱羧氯代反应

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

图式32. 邻二酮的光烷基化/芳基化

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

图式33. 光/镍介导的C(sp3)-C(sp2)交叉偶联

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

图式34. 铜催化介导烷基碘化物的胺化反应

Scheme 34. Copper-catalyzed amination of alkyl iodides

图式35. 铜催化介导的三组分反应

Scheme 35. Copper-catalyzed three-component reactions

图式36. 镍催化亲电试剂的交叉偶联

Scheme 36. Nickel-catalyzed cross coupling of electrophiles

图式37. 光镍协同催化构建氨基甲酰胺化合物

Scheme 37. Cooperative photoredox and nickel catalysis to construct aminoformamides

图式38. 光诱导锰催化烯烃氢氟烃基官能化

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

图式39. 电解启动的镍催化α-氯酸酯与芳基溴之间的对映选择性还原交叉偶联

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

图式40. 氢隧道效应驱动的卤原子转移反应

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

图式41. 卤素原子转移和能量转移实现偶联反应

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

图式42. 三组分SH2反应

Scheme 42. Three-component SH2 reaction

图式43. 可见光诱导的膦催化的烯丙基羧酸酯1,3-碳溴化反应

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

图式44. 可见光诱导的二氟甲基酮脱氟烯丙基化反应

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

图式45. EDA介导合成γ-内酰胺或烯丙基二氟衍生物

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

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