Ethyl 2-O-benzoyl-4,6-O-benzylidene-3-O-naphthylmethyl-1-thio-β-D-glucopyranoside

Ethyl 2-O-benzoyl-4,6-O-benzylidene-3-O-naphthylmethyl-1-thio-β-D-glucopyranoside

Ethyl 2-O-benzoyl-4,6-O-benzylidene-3-O-naphthylmethyl-1-thio-β-D-glucopyranoside is a specialized thioglycoside utilized in carbohydrate chemistry, particularly in the synthesis of complex oligosaccharides and glycoconjugates. Its unique structural features, including protective groups and the thioether linkage, enhance its reactivity and stability during glycosylation reactions.

Chemical Identity

• Molecular Formula: C₃₃H₃₂O₆S
• Molecular Weight: 556.67 g/mol
• CAS Number: 352008-11-8
• Key Functional Groups:
  • Thioether linkage at the anomeric position for enhanced stability and controlled activation.
  • Benzoyl group at the C-2 position for electron-withdrawing effects.
  • Benzylidene acetal protecting the C-4 and C-6 hydroxyl groups to maintain a rigid structure.
  • Naphthylmethyl group at the C-3 position for steric hindrance and influence on reactivity.

Structural Features

1. Thioether Linkage at Anomeric Position:
   • The sulfur atom replaces the typical oxygen in glycosides, forming a thioglycoside that enhances stability during reactions and allows selective activation under mild conditions using promoters such as NIS/TfOH.
2. Protective Groups:
   • The 2-O-benzoyl group stabilizes the compound through an electron-withdrawing effect, which can facilitate neighboring-group participation during glycosylation.
   • The 4,6-O-benzylidene acetal maintains a rigid bicyclic structure, reducing steric hindrance and preventing unwanted side reactions while keeping the hydroxyl groups protected.
   • The 3-O-naphthylmethyl group adds steric bulk, which can influence the selectivity of glycosylation reactions by hindering access to the β-face of the sugar.

Applications

This compound is particularly useful in carbohydrate synthesis due to its unique structural features:

• Glycosylation Reactions: Acts as a glycosyl donor in stereoselective synthesis of oligosaccharides and glycoconjugates. Its thioether linkage allows for activation under mild conditions, enabling controlled formation of glycosidic bonds.
• Intermediate for Complex Molecules: Serves as a precursor in the synthesis of biologically active natural products, glycolipids, and glycoproteins.
• Selective Deprotection Strategies: The benzoyl and benzylidene groups can be selectively removed under specific conditions (e.g., acidic hydrolysis or hydrogenolysis), allowing for further functionalization of the glucopyranoside framework.

Reactivity Profile

The compound’s reactivity is influenced by its protective groups:

• The benzoyl group at O-2 can stabilize reaction intermediates during glycosylation, while the bulky naphthylmethyl group can enhance selectivity by obstructing certain reaction pathways.

Physical Properties

• Appearance: Typically a crystalline solid or powder.
• Solubility: Soluble in common organic solvents like dichloromethane or chloroform due to its hydrophobic protective groups.

This compound exemplifies advanced design in carbohydrate chemistry, offering tailored reactivity for constructing complex oligosaccharides and glycoconjugates with applications in medicinal chemistry and materials science.

Citations:

1. https://www.chemicalbook.com/ChemicalProductProperty_EN_CB63169759.htm
2. https://www.beilstein-journals.org/bjoc/content/supplementary/1860-5397-14-95-S1.pdf
3. https://pubs.acs.org/doi/10.1021/acs.joc.7b00065
4. https://pmc.ncbi.nlm.nih.gov/articles/PMC2696688/
5. https://www.sigmaaldrich.com/IN/en/product/achemblock/advh99c10105
6. https://www.sigmaaldrich.com/IN/en/product/chemscenellcpreferredpartner/ciah987f1f51
7. http://accelachem.com/cn/productview_goodsid_519661_goodscode_SY249843.html
8. https://synthose.com/products/EG501