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

doi:10.6023/cjoc202408001

Abstract

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

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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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Fig. & Tab. 32

Scheme 1. Visible light promoted deoxygenative arylation reaction of oxalates

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

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

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

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

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

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

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

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

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

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

Scheme 12. Photoinduced C-arylation of glycosyl compounds

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

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

Scheme 15. Photoexcited deoxycoupling reaction of aryl nitrile and alcohols

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

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

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

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

Scheme 20. Mechanism of diradicals couple-close reaction

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

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

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

Scheme 24. Deoxygenatve arylation of alcohols via phosphoranyl radical intermediates

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

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

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

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

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

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

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

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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Fig. & Tab. 32

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