Effective and chemoselective glycosylations using 2,3-unsaturated sugars.
Glycosyl donors containing a double bond between C2 and C3 were designed by mimicking the reaction mechanism of lysozyme-initiated hydrolysis of mucopolysaccharides. It was found that, under various glycosylation conditions, the reactivities of 2,3-unsaturated glycosyl acetates were significantly higher, while those of the corresponding 2,3-unsaturated-4-keto glycosyl acetates were much lower than those of the corresponding 2,3-dideoxy (2,3-saturated) glycosyl acetates. Based on these results, chemoselective glycosylations were effectively realized via combinatorial techniques in short-steps using three types of glycosyl donors to construct several types of deoxyoligosaccharides. Furthermore, the highly reactive 2,3-unsaturated glycosyl acetates were found to be useful in the synthesis of the O-glycosides of low reactive tertiary alcohols.
Kusumi
Shunichi
S
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522, Japan.
Sasaki
Kaname
K
Wang
Sainan
S
Watanabe
Tatsuya
T
Takahashi
Daisuke
D
Toshima
Kazunobu
K
D000085:Acetates / Q000737:chemistry; D000438:Alcohols / Q000737:chemistry; D002241:Carbohydrates / Q000138:chemical synthesis / Q000737:chemistry*; D006031:Glycosylation; D007661:Ketoses / Q000138:chemical synthesis / Q000737:chemistry; D009844:Oligosaccharides / Q000138:chemical synthesis / Q000737:chemistry; D013379:Substrate Specificity
D000085:Acetates; D000438:Alcohols; D002241:Carbohydrates; D007661:Ketoses; D009844:Oligosaccharides