光/电促进醇及其衍生物C—O键活化构筑C(sp2)—C(sp3)键研究进展

doi:10.6023/cjoc202408001

摘要/Abstract

开发经济、高效和实用的方法来构建C(sp²)—C(sp³)键一直是合成化学的一个中心课题. 近年来, 在光化学和电化学合成中, 过渡金属催化的C(sp²)—C(sp³)交叉偶联反应由于其官能团兼容性好、反应选择性高及环境友好等优点, 已经成为一个强大的合成手段. 醇是已知分布最广泛、天然含量最丰富的有机化合物之一, 利用醇脱氧产生烷基自由基在有机化学中极具价值. 综述了光/电催化下醇的衍生物, 包括酯类化合物、氮杂环卡宾加合物、膦氧加合物、溴代物以及缩醛与芳基(拟)卤代物C(sp²)—C(sp³)的偶联反应.

关键词: 光化学, 电化学, C(sp²)—C(sp³)偶联反应, 醇衍生物

Developing economical, efficient, and practical methods to construct C(sp²)—C(sp³) bonds has always been a central issue in synthetic chemistry. In recent years, the use of transition metal-catalyzed C(sp²)—C(sp³) cross coupling has become a powerful synthesis method in photochemical and electrochemical synthesis due to its high functional group compatibility, high reaction selectivity and environmental friendliness. Alcohols, as one of the most widely distributed and naturally abundant organic compounds, have great value in organic chemistry in utilizing alcohol deoxygenation to produce alkyl radicals. The C(sp²)—C(sp³) coupling reactions of alcohol derivatives, including esters, N-heterocyclic carbene adducts, phosphine-oxide adducts, bromides and acetals, with aryl (pseudo) halides under photo/electro catalysis are briefly summarized.

Key words: photochemistry, electrochemistry, C(sp²)—C(sp³) coupling reaction, alcohol derivative

引用此文

张艮红, 余若曦, 陈跃刚. 光/电促进醇及其衍生物C—O键活化构筑C(sp²)—C(sp³)键研究进展[J]. 有机化学, 2025, 45(5): 1548-1568.

Genhong Zhang, Ruoxi Yu, Yuegang Chen. Research Progress in Photo/Electro-Induced C(sp²)—C(sp³) Bond Construction by Activating C—O Bond of Alcohols and Their Derivatives[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1548-1568.

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图/表 32

图式1. 可见光促进的草酸酯的脱氧芳基化反应

Scheme 1. Visible light promoted deoxygenative arylation reaction of oxalates

图式2. 可见光促进的草酸酯与溴苯的交叉偶联反应机理

Scheme 2. Cross coupling reaction mechanism of oxalates and aryl bromide promoted by visible light

图式3. 紫外光促进的草酸铯的脱氧minisci反应

Scheme 3. Ultraviolet light promoted deoxygenation of cesium oxalates via minisci-type reaction

图式4. 紫外光促进的草酸铯盐与对苯二腈minisci反应机理

Scheme 4. Minisci-type reaction mechanism of cesium oxalates and p-phenylenediamine promoted by ultraviolet light

图式5. 醇、炔烃和溴苯的三组分偶联反应

Scheme 5. Three component coupling reaction of alcohols, alkynes, and aryl bromide

图式6. 醇、炔烃和溴苯的三组分偶联反应机理

Scheme 6. Mechanism of three component coupling reaction of alcohols, alkynes, and aryl bromide

图式7. 光/镍催化C—O键烯基化/C—H键芳基化反应机理

Scheme 7. Mechanism of C—O bond olefinization/C—H bond aromatization catalyzed by light/nickel

图式8. 光镍催化C—O键活化实现烯烃烷基芳基化反应

Scheme 8. Activation of C—O bonds catalyzed by photoredox and nickel catalysis for alkylarylation of olefins

图式9. 可见光促进的硅自由基介导的交叉偶联反应机理

Scheme 9. Mechanism of visible light promoted silicon radical mediated cross coupling reaction

图式10. 光促对氰基吡啶与醇的脱氧偶联合成小分子与DNA编码库

Scheme 10. Photoinduced deoxygenative coupling of p-cyanopyridine and alcohols for synthesis of small molecules and DNA-encoded libraries

图式11. 无金属催化对氰基吡啶与醇的脱氧偶联反应机理

Scheme 11. Mechanism of metal-free catalyzed deoxygenative coupling of p-cyanopyridine and alcohols

图式12. 光促糖基化合物C-芳基化反应

Scheme 12. Photoinduced C-arylation of glycosyl compounds

图式13. 二氢吡啶(DHP)介导的醇的衍生物C—O键活化反应机理

Scheme 13. Mechanism of C—O bond activation reaction of alcohol derivatives mediated by DHP

图式14. 仲丁基自由基引发的黄原酸苄酯与缺电子溴苯交叉偶联反应及机理

Scheme 14. Reaction and mechanism of benzyl xanthates with electron deficient bromobenzenes initiated by sec-butyl radical

图式15. 光激发芳香腈与醇的脱氧偶联反应

Scheme 15. Photoexcited deoxycoupling reaction of aryl nitrile and alcohols

图式16. 对苯二腈与醇的衍生物的脱氧自由基偶联反应机理

Scheme 16. Mechanism of deoxygenation radical coupling reaction between alcohol derivatives and p-phenylenediamine

图式17. 氮杂环卡宾介导的烷基醇的脱氧芳基化反应

Scheme 17. Deoxygenative arylation reaction of alkyl alcohols mediated by N-heterocyclic carbenes

图式18. 氮杂环卡宾介导的脱氧芳基化的反应机理

Scheme 18. Mechanism of N-heterocyclic carbenes mediated deoxygenative arylation

图式19. 双官能团前体与吡啶溴代物环化反应

Scheme 19. Couple-close reaction of bifunctional precursor with pyridine bromides

图式20. 双自由基偶联-关环反应机理

Scheme 20. Mechanism of diradicals couple-close reaction

图式21. 溴苯与NHC-醇加合物的不对称脱氧交叉偶联

Scheme 21. Enantioselective deoxygenative cross coupling of NHC-alcohols and aryl bromide

图式22. 电催化醇与芳香腈的C(sp2)—C(sp3)脱氧偶联反应

Scheme 22. Electrocatalytic C(sp3)—C(sp2) deoxygenative coupling reaction of alcohols and aromatic nitriles

图式23. 电促醇的脱氧芳基化反应机理

Scheme 23. Mechanism of deoxygenative arylation of alcohols promoted by electricity

图式24. 磷酰自由基中间体实现的醇的脱氧芳基化反应

Scheme 24. Deoxygenatve arylation of alcohols via phosphoranyl radical intermediates

图式25. 外源碘自由基加成实现P-O加合物脱氧转化机理

Scheme 25. Mechanism of P-O adduct deoxygenaive transformation via exogenous radical addtion

图式26. 电促镍催化的醇与芳基卤代物的脱氧偶联反应

Scheme 26. Electrochemically enabled nickel-catalyzed deoxygenative coupling reaction of alcohols and aryl halides

图式27. 电/镍催化醇原位溴化脱氧偶联反应机理

Scheme 27. Mechanism of electro/nickel-catalyzed in situ bromination deoxygenative coupling reaction of alcohols

图式28. 光/镍催化醇原位溴化脱氧偶联反应及机理

Scheme 28. Photoredox/nickel-catalyzed in situ bromination deoxygenative coupling reaction of alcohols and itsmechanism

图式29. 可见光促进的芳基氯化物C(sp2)—C(sp3)偶联反应

Scheme 29. Visible light promoted C(sp2)—C(sp3) coupling reaction of aryl chloride

图式30. 氯自由基介导的缩醛类化合物C—O键活化机理

Scheme 30. Mechanism of chlorine radicals mediated C—O bond activation in acetal compounds

图式31. 溴自由基介导的缩醛类化合物C—O键活化反应及机理

Scheme 31. Reaction and Mechanism of bromine radicals mediated C—O bond activation in acetal compounds

图32. 环状缩醛作为C(sp3)部分C—O键活化

Scheme 32. Cyclic acetal as part of C(sp3) for C—O bond activation

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光/电促进醇及其衍生物C—O键活化构筑C(sp²)—C(sp³)键研究进展

Research Progress in Photo/Electro-Induced C(sp²)—C(sp³) Bond Construction by Activating C—O Bond of Alcohols and Their Derivatives

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