The application of 2, 2, 2-trichloroethyl sulfate to the synthesis of chondroitin sulfate C and D. (10th April 2015)

• Record Type: Journal Article
• Authors: Matsushita, Kenya; Nakata, Tomomi; Tamura, Jun-ichi
• Is Part Of: Carbohydrate research. Volume 406(2015)
• Page Start: 76
• Page End: 85
• Publication Date: 2015-04-10
• Subjects: Protected sulfate -- Sulfated oligosaccharide -- Glycan synthesis; BAIB bisacetoxyiodobenzene -- CS chondroitin sulfate -- MS molecular sieves -- SDIS 2, 2, 2-trichloroethoxysulfuryl-1, 2-dimethylimidazolium triflate -- TBAF tetra-n-butylammonium fluoride -- TEMPO 2, 2, 6, 6-tetramethylpiperidine 1-oxyl -- TCE 2, 2, 2-trichloroethyl -- TMSOTf trimethylsilyl triflate; Carbohydrates -- Periodicals; Chemistry, Organic -- Periodicals; Biochemistry -- Periodicals; Carbohydrates -- Periodicals; Chimie organique -- Périodiques; Glucides -- Périodiques; Biochemistry; Carbohydrates; Chemistry, Organic; Periodicals; Electronic journals; 507.78
• DOI: 10.1016/j.carres.2015.01.007
• Languages: English
• ISSNs: 0008-6215

Abstract

Abstract: Chondroitin sulfates (CSs) have characteristic bioactivities that depend on sulfation patterns. Chemically synthesized CS oligosaccharides are valuable tools for elucidating the relationship between structures and bioactivities. 2, 2, 2-Trichloroethyl (TCE) sulfated sugars are highly soluble in nonpolar solvents, which is useful for the synthesis of sulfated oligosaccharides. We herein synthesized CS-C [βGalNAc6S(1–4)βGlcA] (1 ) and CS-D [βGalNAc6S(1–4)βGlcA2S] (2 ) disaccharides that possessed sulfate groups by TCE sulfation at O-6 of GalNAc and an additional sulfate group at O-2 of GlcA, respectively. We revealed the superior functionalities of TCE sulfates during the synthesis of CS-C and -D, despite the unwanted side reactions in the acetamido-containing substrate. Graphical abstract: We synthesized CS-C [βGalNAc6S(1–4)βGlcA] (1 ) and CS-D [βGalNAc6S(1–4)βGlcA2S] (2 ) disaccharides that possessed sulfate groups by 2, 2, 2-trichloroethyl sulfation at O-6 of GalNAc and an additional sulfate group at O-2 of GlcA, respectively. Highlights: We first applied TCE sulfate to the synthesis of chondroitin sulfate C and D. TCE sulfate also acted as a good leaving group. TCE sulfate in acetamido-containing substrate caused side reaction. TCE sulfate is an applicable tool for the synthesis of sulfated oligosaccharides.