Synthetic Routs of Carbon Glycosides:

1. Diastereocontrolled Synthesis of Carbon Glycosides of N-

Acetylneuraminic Acid via Glycosyl Samarium(III)
Intermediates
 2. Synthesis and in vitro biological evaluation of a carbon
glycoside analogue of morphine-6-glucuronide:

Reagents and conditions: (i) CH3S(O)CH3, Ac2O; (ii) LiCH2CO2Et, THF then HCl, _78
_C to rt; (iii) Et3SiH, BF3ÆOEt2,CH3CN, 0 _C to rt; (iv) NaOH, H2O, THF, reflux then
HCl; (v) SOCl2; (vi) 3-O-triisopropylsilyl-6-b-aminomorphine, Et3N, CH2Cl2; (vii) Bu4NF,
THF, H2O; (viii) H2, 10% Pd–C, MeOH; (ix) H2, 10% Pd–C, MeOH, HCl.
3. The Chemical Enzymatic Synthesis of a Carbon Glycoside of
N Acetyl Neuraminic acid:
 4. Synthesis of Beta C-Glycosides using Anomeric
Trichloroacetimidates:

Schemit and his coworkers used anomeric trichloroacetimidates as glycosyl donors

for the synthesis of beta C-glycosides especially in C-glycosidation.

5. C-glycosilation through Anomeric Anoinic Intermediates:

Kessler used Reductive lithiation dianion method for the synthesis of Carbon glycosides.
6. Synthesis of C-glycopeptides from amino sugars using
Reductive Lithiation dianion method:

7. Synthesis of C-glycosides from Alkoxyvinyl deprotonation:

The addition of lithiated glycal derivative to uinol ketal or quinone then aromatization
and hydroboration produce C-aryl arabinofuranosides. The 3,4 trans disubtituted
dihydrofuran derivative gives alpha C-glycoside while cis isomer gives beta C-
xylofuranoside.
8. Synthesis of C-glycosides from Alkoxyvinyl deprotonation:

Schemit and coworkers used C2 sulfoxide stabilized 1C lithiated glucal as

nucleophile.Its reaction with various aldehydic electrophile produce hydroxyl
methylene bridged Carbon glycosides.
9. Synthesis of a C-Glycoside Analogue of sTn: An HIV- and
Tumor-Associated Antigen:

Scheme . Synthesis of sTn C-glycoside derivatives. a) Ph3P, I2, Im;

b) KCN; c) DIBAL-H; d) NaBH4; e)H+ resin; f) Ac2O, HBr/HOAc;
g) excess HBr/HOAc; Zn/Cu; i) CAN, NaN3 ; j) LiBr; k) Z-Ser-OBn,
AgClO4, 4D molecular sieves; l) AcSH/Py; m) R. toruloides, sodium
phosphate/sodium citrate buffer, pH 5; n) DMSO, ClCOCOCl, TEA;
o) SmI2 ; p) DMSO/Ac2O; q) Zn(BH4)2. R1=Bn. Im=imidazole,
DIBAL-H=diisobutylalumininum hydride, Py=pyridine, TEA=triethylamine,
DMSO=dimethyl sulfoxide
 10. Synthesis of C- glycosylpyrrolo [3,4-c] carbazole 1,3(2H,6H)
diones.

Glycals are attached with aryl moiety in Heck coupling reaction under different conditions.
Matsuda and co-workers worked on the synthesis of indolocarbazole , a potential checkpoint
kinase 1 inhibitor, comprising Heck reaction then followed by a 6 electron cyclization.
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111111111
 11. Synthesis of C-glycoside by Negishi cross coupling
approach:
C-glycoside can be synthesised by Negishi coupling reaction of an organozinc compound and an
organic halide, nickel or palladium complexes are used as catalyst. Glycals and glycosyl halides
can be used as starting materials for Negishi cross coupling reaction.

12. 12. Synthesis of 2-aryl-3-hydroxy-6-(hydroxymethyl)pyrans.

Hayashi and co-workers developed an asymmetric synthesis of optically active cis- and
trans-2-aryl-6-methylpyrans from commercially available tetra-O-acetyl-D
glucopyranosyl bromide.
 13. Additions of allylsilanes:

Horton reported the synthesis of 3 (2,3,4,6-tetra-O-acetyl-a_D-glucopyranosyl) propene 8 and 9

in 23% combined yield with ratio 5:1.

14. Stereoselective allylation of 1-alkylglucal

Nicolaou and co-workers reported the stereoselective allylation at the C-1 position in 1-
alkylglucal 10 using TiCl4 to get compound 11
 15. Ferrier type alkynylation of glucals using activated alkynes.

Ferrier type alkynylation of glucals by using activated alkynes vi allyltrimethylsilane as

nucleophile.Reaction occure in the presence of ZrCl4, HClO4-SiO2, Er(OTf)3, TMSOTf,
AuCl3 or Zeolite which leads to the formation of products in high yield with good -
selectivity.

16. Stereoselective C-glycosylation of glycal using unactivated

alkynes.

Mukherjee and co-workers reported a stereoselective C-glycosylation reaction between

glycal 14 and unactivated alkynes 15 in the presence of copper triflate and ascorbic acid to
synthesize the C-glycosides 16.
 17. Radical addition method: Addition of ethyl bromodifluoroacetate to 2-
benzyloxyglucal.

Radical addition between highly electrophilic radicals (fluorinated or unfluorinated) and 2-

benzyloxyglucal or galactal gives a new path for the synthesis of C-glycosides.

18. Knoevenagel condensation: Synthesis of b-C-glycosides.

Recently Wang developed a stereoselective procedure for the preparation of ketone -C-
pyranosides 21 and ketone -Cfuranosides 22 upon condensation of pentane-2,4-dione
with various unprotected sugars 20 in presence of sodium carbonate in water. At 90 ºC, the
ketone -C-pyranoside 21 was obtained in excellent yields (up to 97%) in short reaction
time. In contrast, at 10 ºC, the ketone C-furanosides, 24 were the main products obtained in
83-97% yield.
 19. Ruthenium catalyzed synthesis of 2,3-unsaturated C-
glycosides from glycals:

A highly effective and commodious C-glycosylation method was developed using

ruthenium(III) chloride for the synthesis of 2,3-unsaturated C-glycosides. Different nucleophiles
such as allyl trimethylsilane, triethylsilane, trimethylsilyl cyanide, trimethylsilyl azide and
heterocycles such as thiophene and furan reacted efficiently with glycals in the presence of
catalytic amount of ruthenium trichloride under mild reaction conditions.
 20. Synthesis of densely functionalised C-glycosides by a tandem oxy
Michael addition–Wittig olefination pathway:

Wittig olefination of 5,6-dideoxy-5,6-anhydro-6-nitro-D-glucofuranose (5) triggered a

concomitant cyclisation via oxy Michael addition of the C2-hydroxyl group resulting in the
formation of C-vinyl glycosides with Z-olefinic geometry.
 21. Aldol reaction of b-C-glycosylic ketones: synthesis of
C-(E)-cinnamoyl glycosylic compounds as precursors
for new biologically active C-glycosides:

22. 1-C-(20-Oxoalkyl) glycosides as latent a,b unsaturated

conjugates.Synthesis of aza-C-glycosides by an intramolecular
hetero-Michael addition:

Scheme#1
Scheme#2

Scheme#3

Scheme#4
23. Synthesis of a Carbon-Linked Mimic of the Disaccharide
Component of the Tumor-Related SialylTn Antigen:

24. Synthesis of various C glycofuranosyl glycines:

25. The synthesis of a â-linked C- galactosyl L-serine:

26. The coupling between the iodomethyl C-glucoside

and the chiral thiol :
 27. The synthesis of three â-linked C-glycosyl Lasparagines
(D-galacto, D-gluco, D-manno,) starting from the formyl C-glycosides.

28. C-glycosyl asparagine:

29. Aluminum- and Boron-Mediated C-Glycoside Synthesis
from 1,2-Anhydroglycosides:

30. Regioselective Synthesis of Unsymmetrical C-Aryl

Glycosides Using Silicon Tethers as Disposable Linkers:
31. Stereospeci®c synthesis of _-C-glycosyl derivatives (C-
glycosides'') of N-acetylneuraminic acid by samarium-mediated
reductive desulfonylation of a glycosyl phenylsulfone:

32. Preparation of r-C-Glycosides from Glycals:

33. Preparation of Enone-Type C-Glycosides with DDQ as the
Oxidant:

34. Synthesis of C-Aryl and C-Alkyl Glycosides Using Glycosyl

Phosphates:
35. Synthesis and Conformational Analysis of Carbon
Trisaccharides:
36. Sigmatropic Rearrangements for synthesis of C- Glycosides:

37. Claisen rearrangement for the synthesis of C- Glycosides

38. Wittig rearrangement for C-glycoside synthesis:

39. C-glycoside synthesis via cycloaddition:

40. C-glycoside synthesis via Diels elder reaction:

41. Reactions of Hemiacetals followed by Ring Closure Wittig
approach to C Glycoside synthesis:

42. Reaction of L.uctones for C Glycoside synthesis:

43. Reactions of Anomeric Phosphoranes:

44. PALLADIUM MEDIATED REACTIONS: C Glycoside

synthesis from Allyl Complexes:

45. PALLADIUM MEDIATED REACTIONS: C Glycosides

synthesis Heck type coupling :
46. C-Glycosides coupling reactions synthesis from Mitsonobu:

47. Glycoside synthesis from Glycosides:

48. Synthesis of monosubstitutedcalix[4]pyrrole.

49. Synthesis of C-Glycosides from glycosyl Halide:

50. C-Glycosides Synthesis from Enitols & Anhydro Sugars: