Synthetic 3-O-methylmannose-containing polysaccharides (sMMPs): design and synthesis.
With the hope of mimicking the chemical and biological properties of natural 3-O-methylmannose-containing polysaccharides (MMPs), synthetic 3-O-methylmannose-containing polysaccharides (sMMPs) were designed and synthesized in a convergent manner. With little modification of the Mukaiyama glycosidation, high alpha-selectivity (>50:1 approximately >20:1) and yields (79 approximately 74%) were achieved for the key glycosidation steps. The exceptionally high alpha-selectivity observed was shown to be consequent to the selective anomerization of beta- to alpha-anomer under the glycosidation conditions. This glycosidation is well suited for a highly convergent oligosaccharide synthesis, particularly because of excellent chemical yields even when using approximately equal-sized donors and acceptors in an approximately 1:1 molar ratio. An iterative reaction sequence allowed the growing oligosaccharide to double in size after each cycle and led to an efficient synthesis of sMMP 8-, 12-, and 16-mers 18-20.
Hsu
Margaret C
MC
Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford Street, Cambridge, Massachusetts 02138, USA.
Lee
Jinhwa
J
Kishi
Yoshito
Y
D015195:Drug Design; D006031:Glycosylation; D008766:Methylmannosides / Q000737:chemistry*; D018716:Molecular Mimicry; D009844:Oligosaccharides / Q000138:chemical synthesis; D011134:Polysaccharides / Q000138:chemical synthesis*
D008766:Methylmannosides; D009844:Oligosaccharides; D011134:Polysaccharides; C043123:3-O-methylmannose