Photoredox-Catalyzed C-Glycosylation Reactions

doi:10.6023/cjoc202408003

Abstract

Photoredox catalysis has become a multifunctional and efficient reaction method for constructing C-glycosides, which provides a new pathway for synthesizing complicated carbohydrate. This mild green synthetic tool has been used to synthesize C-glycosides with diverse functional groups, which has a promoting effect on carbohydrate chemistry research. The types of C-glycosidic reactions constructed through photoredox catalysis, which are categorized as a conventional photoredox catalysis, redox reactions involving excited-state transition metals, dual photoredox/transition metal (TM)-catalyzed cross- coupling reaction and light-excited electron donor-acceptor complex, are systematically summarized. In addition, a detailed description of the reaction mechanisms is provided.

Key words: photoredox catalysis, glycosylation, C-glycosylation, glycosyl radical

Cite this article

Chen Li, Yi Jiao, Xiaoran Shi, Yiqiang Yang, Shouyun Yu. Photoredox-Catalyzed C-Glycosylation Reactions[J]. Chinese Journal of Organic Chemistry, 2025, 45(5): 1423-1459.

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Fig. & Tab. 52

Figure 1. Representative compounds of C-glycosides

Scheme 1. Glycosyl radical-mediated C-glycosylation

Scheme 2. Main pathways of photoredox-catalyzed C-glycosylation reaction

Scheme 3. Visible-light-mediated alkylation reaction of glycosyl bromides with olefins

Scheme 4. Photomediated defluorinative gem-difluoroallylation reaction

Scheme 5. Glycosylation of peptide Dha by glycosyl bromides

Scheme 6. Synthesis of α-C-glycosyl alanine analogues

Scheme 7. Visible-light-induced glycoarylation of activated olefins

Scheme 8. C-Alkylation of alcohols

Scheme 9. Site-selective alkylation of unprotected monosaccharides

Scheme 10. Deformylative 1,4-addition to synthesize 5'-carba analogs of nucleoside 5'-phosphates

Scheme 11. Synthesis of C-glycosyl amino acids

Scheme 12. Decarboxylative photoalkylation of glycosyl NHP esters via inversion of stereochemistry

Scheme 13. Photoredox catalytic site- and stereoselective C—H alkylations

Scheme 14. Photoredox catalytic regioselective C—H alkylation of fructopyranose derivative

Scheme 15. C-Glycosylation of glycosyl sulfinates and Michael acceptors

Scheme 16. Photoredox-catalyzed synthesis of carbohydrate-DNA conjugates

Scheme 17. Stereoselective alkyl C-glycosylation of glycosyl esters via anomeric C—O bond homolysis

Scheme 18. Site-selective C-alkylation of unprotected sugars

Scheme 19. Direct C—H trifluoromethylation of glycal

Scheme 20. Reductive fluoroalkylation of 2-acetoxyglycas

Scheme 21. Direct C—H trifluoromethylation of glycals

Scheme 22. Alkenylation of unactivated glycosyl bromides through visible light photocatalysis

Scheme 23. Photoredox-catalyzed vinylations of glycosyl-dihydropyridines (DHPs) and vinylbenziodoxol(on)es

Scheme 24. Photoredox-catalyzed reductive coupling of glycosyl bromides to access C-alkynyl glycosides

Scheme 25. Stereoselective C-glycosylation by photocatalytic decarboxylative alkynylation

Scheme 26. Synthesis of heteroaryl C-glycosides via 4-glycosyl-dihydropyridines

Scheme 27. Synthesis of C-nucleoside analogues from glycosyl bromides and heteroarenes under visible light

Scheme 28. C-heteroaryl glycosylation of biphenyl isocyanides/ 2-isocyanoaryl selenoethers/thioethers with glycosyl bromides

Scheme 29. Visible-light-induced Pd-catalyzed Heck-type radical reactions to construct C-alkenylation glycosides

Scheme 30. Excited-state palladium-catalyzed methods to construct C-ketonylation glycosides

Scheme 31. Visible-light-promoted and Cu-catalyzed stereoselective C-glycosylation

Scheme 32. Synthesis of highly functionalized arylated saccharides through nickel/photoredox dual catalysis

Scheme 33. Synthesis of aryl/ heteroaryl-C-nucleosides via Ni/photoredox-catalyzed decarboxylation

Scheme 34. Ni/photoredox dual catalytic coupling of glycosyl trifluoroborates

Scheme 35. Ni/photoredox dual catalytic deoxygenative arylation of alcohols

Scheme 36. Ni/photoredox dual catalytic reductive cross-coupling of glycosyl chlorides and aryl bromides

Scheme 37. Ni/photoredox dual catalytic reductive cross-coupling of glycosyl chlorides and aryl bromides

Scheme 38. Ni/photoredox dual catalytic reductive cross-coupling of pyranosyl bromides with 3-methoxycarbonyl-2-iodo-1H-indoles

Scheme 39. Synthesis of unprotected aryl C-glycosides by photoredox/Ni-catalysed cross-coupling

Scheme 40. Regioselective nickel-catalyzed photoredox allylation of secondary α-alkoxy radical precursors

Scheme 41. Photoredox/nickel dual catalytic Tsuji-Trost reaction of allylic alcohols

Scheme 42. Photoredox/Cu dual catalytic reaction for construction of C-linked glycosides and glycopeptides

Scheme 43. Synthesis of alkynyl C-nucleosides from furanosyl carboxylic acids and terminal alkynes under photoredox/nickel dual catalysis

Scheme 44. Synthesis of C-acyl glycosides through Ni/photoredox dual catalysis

Scheme 45. Mechanism of the synthesis of C-acyl glycosides through Ni/photoredox dual catalysis

Scheme 46. Nickel-mediated preparation of nonanomeric C-acyl-saccharides through EDA complex photoactivation

Scheme 47. Synthesis of amide linked C-glycosyl amino acids and peptides throught Ni/photoredox dual catalysis

Scheme 48. Visible-light promoted EDA complex to enable pyridine functionalization of galactopyranose modified with 1,4-DHPs

Scheme 49. Glycosyl sulfoxides as radical precursors and their use in the synthesis of pyridine derivatives

Scheme 50. Visible light activation enabled desulfonylative of heteroaryl glycosyl sulfone substrates to couple with electrophiles

Scheme 51. Direct radical functionalization of native sugars

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光氧化还原催化的C-糖基化反应