Mild synthesis of disaccharidic 2,3-enopyranosyl cyanides and 2-C-2-deoxy pyranosyl cyanides with Hg(CN)(2)/HgBr(2)/TMSCN.
Lewis acid-catalyzed dimerization of mono- and disaccharidic per-O-acetylated glycals gave di- and tetrasaccharidic O-acetylated C-glycosides, respectively. 2,3-Enopyranosyl cyanides were obtained from per-O-acetylated glycals by a new, mild anomeric S(N)'-acetoxy displacement with Hg(CN)(2)/HgBr(2)/TMSCN. Per-O-acetylated 2-C-2-deoxy-pyranoses were converted into pyranosyl cyanides by the same reagent. An unprecedented acetic acid elimination from dimers with D-galacto- and L-fuco-configurations accompanied the S(N)-displacement under those conditions. A new set of (1)H NMR coupling constants for 2,3-enopyranosyl systems was used for configurational assignment of complicated tetrasaccharide mimics.
Franz
Andreas H
AH
Department of Chemistry, University of the Pacific, 3601 Pacific Avenue, Stockton, California 95211, USA.
Wei
YiQiu
Y
Samoshin
Vyacheslav V
VV
Gross
Paul H
PH
D000107:Acetylation; D002475:Cellobiose / Q000031:analogs & derivatives* / Q000737:chemistry; D003486:Cyanides / Q000138:chemical synthesis* / Q000737:chemistry*; D003847:Deoxyglucose / Q000031:analogs & derivatives* / Q000737:chemistry; D019281:Dimerization; D004187:Disaccharides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008628:Mercury / Q000737:chemistry*; D015394:Molecular Structure
D003486:Cyanides; D004187:Disaccharides; D002475:Cellobiose; C043334:3,4,6-tri-O-acetylglucal; C048667:cellobial; D003847:Deoxyglucose; D008628:Mercury