Synthesis of beta-analogues of C-mannosyltryptophan, a novel C-glycosylamino acid found in proteins.
alpha-C-Mannosyltryptophan (alpha-C-Man-Trp) has been found to be a novel post-translational modification of tryptophan found from some biologically important glycoproteins. In order to analyze the biological functions of alpha-C-Man-Trp, we have developed an efficient synthetic strategy for alpha-C-Man-Trp and its glucose and galactose analogues, starting from alpha-C-glycosidation of the corresponding hexapyranoside derivatives with tinacetylene. According to the synthetic routes, we describe here syntheses of beta-anomers of C-Man-Trp, and its glucose and galactose analogues from the corresponding beta-C-glycosylacetylenes. During this study, we have developed a highly stereocontrolled synthesis of beta-C-mannosylacetylene that is required for the synthesis of beta-C-Man-Trp, while the precedented method gave an anomeric mixture of the C-mannosylacetylene. The synthetic C-Man-Trp and its analogues were analyzed by HPLC.
Nishikawa
Toshio
T
Laboratory of Organic Chemistry, Graduate School of Bioagricultural Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan. nisikawa@agr.nagoya-u.ac.jp
Koide
Yuya
Y
Kanakubo
Akira
A
Yoshimura
Hiroshi
H
Isobe
Minoru
M
D002236:Carbohydrate Conformation; D005690:Galactose / Q000737:chemistry; D005947:Glucose / Q000737:chemistry; D006031:Glycosylation; D009682:Magnetic Resonance Spectroscopy; D008358:Mannose / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D009904:Optical Rotation; D011506:Proteins / Q000737:chemistry*; D013055:Spectrophotometry, Infrared; D014364:Tryptophan / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry
C101500:C(2)-mannosyltryptophan; D011506:Proteins; D014364:Tryptophan; D005947:Glucose; D008358:Mannose; D005690:Galactose