Recent Progress on the Construction of C(sp2)—C(sp3) Bonds via Photoredox/Nickel Dual Catalysis

doi:10.6023/cjoc202504001

Abstract

The photoredox/transition metal dual catalysis system has emerged as a pivotal research direction in modern organic synthesis. Recent breakthroughs have been achieved in dual catalytic systems centered on earth-abundant nickel and integrated with photoredox catalysis. This system efficiently converts diverse alkyl radicals precursors through photochemical processes under mild reaction conditions and demonstrates remarkable advantages in the selective construction of C(sp²)—C(sp³) bonds. Notably, the synergistic mechanism between photocatalytic generation of alkyl radical species and nickel-catalyzed C(sp²)—C(sp³) cross-coupling not only expands the substrate scope of cross-coupling reactions, but also unlocks novel pathways for the conversion of bulk chemicals into high-value-added fine chemicals. This review summarizes the research progress in this field, highlighting the diverse sources of alkyl radical precursors and discussing key catalytic mechanisms.

Key words: photoredox catalysis, nickel catalysis, dual catalysis, alkyl radical, C(sp²)—C(sp³) bonds

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Genwei Gao, Zhen Li, Yan Li, Xi Lu. Recent Progress on the Construction of C(sp²)—C(sp³) Bonds via Photoredox/Nickel Dual Catalysis[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 1905-1919.

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Fig. & Tab. 29

Scheme 1. Photoredox/nickel dual catalytic reactions involving different alkyl radical generation mechanisms

Scheme 2. Dual catalysis of photoredox/nickel for the coupling reaction of alkyl carboxylic acids with aryl halides

Scheme 3. Enantioselective decarboxylative arylation of α-amino acids

Scheme 4. Decarboxylative cross-coupling enabled by Fe and Ni metallaphotoredox catalysis

Scheme 5. Metallaphotoredox-enabled deoxygenative arylation of alcohols

Scheme 6. Cross-coupling of organoboron enabled by photoredox/nickel dual catalysis

Scheme 7. Visible-light photocatalytic cross-coupling of bis-catecholato silicon compounds

Scheme 8. Cross-coupling reaction of alkenyl halides with alkylsilicates via photoredox/nickel dual catalysis

Scheme 9. Enantioselective three-component carboarylation of alkenes enabled by photoredox/nickel dual catalysis

Scheme 10. Cross-coupling reaction of aryl halides with 4-alk-yl-1,4-dihydropyridines via photoredox/nickel dual catalysis

Scheme 11. Cross-coupling of 1,4-dihydropyridine derived from aldehyde with aryl bromides

Scheme 12. Photoredox/nickel dual catalysis containing single electron reduction to generate alkyl radicals

Scheme 13. NEt3 driven photoredox/nickel dual catalysis for cross-electrophile coupling of aryl bromide and alkyl bromide

Scheme 14. Reductive cross-coupling of aryl halides with dichloromethane via photoredox/nickel dual catalysis

Scheme 15. Access to chiral α-aryl phosphates via dual nickel-and photoredox-catalyzed reductive cross-coupling

Scheme 16. Preparation of C-aryl glycosides via visible-light induced nickel-catalyzed reductive cross-coupling of glycosyl chlorides and aryl bromides

Scheme 17. Metallaphotoredox-catalyzed enantioselective cross-electrophile coupling using alcohols as reducing agents

Scheme 18. Cross-electrophile coupling of metal photocatalytic oxidation-reduction activated by silicon-based radicals

Scheme 19. Cross-electrophile coupling of unactivated alkyl chlorides

Scheme 20. Cross-coupling of dimethylaniline with aryl halides to generate α-arylaniline via photoredox/nickel dual catalysis

Scheme 21. C(sp3)—H functionalization of amines with aryl halides by photoredox/nickel dual catalysis

Scheme 22. Direct acylation of C(sp3)—H bonds enabled by nickel/photoredox dual catalysis

Scheme 23. Direct arylation of strong aliphatic C(sp3)—H bonds

Scheme 24. Stereoselective and site-divergent synthesis of C-glycosides

Scheme 25. Triple catalytic alkylative cross-coupling of C(sp3)—H bonds

Scheme 26. Direct C(sp3)—H cross coupling enabled by catalytic generation of halogen radicals

Scheme 27. Mechanism investigation of nickel-catalyzed photochemical halogen atom-mediated C(sp3)—H arylation

Scheme 28. Direct enantioselective C(sp3)—H acylation for the synthesis of α-amino ketones

Scheme 29. C(sp3)—H arylation enabled by the synergy of triplet excited ketones and nickel catalysts

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光/镍协同催化C(sp²)—C(sp³)键构建研究进展

Recent Progress on the Construction of C(sp²)—C(sp³) Bonds via Photoredox/Nickel Dual Catalysis

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Fig. & Tab. 29

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光/镍协同催化C(sp2)—C(sp3)键构建研究进展