Ohtsuka Isao, Hada Noriyasu, Kanemaru Misaki, Fujii Takanari, Atsumi Toshiyuki, Kakiuchi Nobuko
School of Pharmaceutical Sciences, Kyushu University of Health and Welfare, 1714-1 Yoshino-cho, Nobeoka City, Miyazaki 882-8508, Japan.
Faculty of Pharmacy, Keio University, 1-5-30 Shibakoen, Minato-ku, Tokyo 105-8512, Japan.
Carbohydr Res. 2015 Mar 2;404:9-16. doi: 10.1016/j.carres.2014.11.018. Epub 2014 Dec 3.
The glycosphingolipid neurosporaside (α-D-Glcp-(1 → 2)-β-D-Galp-(1 → 6)-β-D-Galp-(1 → 6)-β-D-Galp-(1 →)-Cer) occurs in Neurospora crassa. We attempted to synthesize neurosporaside by block synthesis (route A) and linear synthesis (route B). Oligosaccharide derivatives were synthesized using trimethylsilyltrifluoromethanesulfonate and N-iodosuccinimide/trifluoromethane sulfonic acid as promoters. The target tetrasaccharide could not be attained via route A, but route B showed potential: glycosidic bonds (β-D-Galp-(1 → 6)-β-D-Galp-(1 → 6)-β-D-Galp) were formed stereoselectively, leading to the synthesis of glycosphingolipid 2.
鞘糖脂神经孢苷脂(α-D-葡萄糖基-(1→2)-β-D-半乳糖基-(1→6)-β-D-半乳糖基-(1→6)-β-D-半乳糖基-(1→)-神经酰胺)存在于粗糙脉孢菌中。我们尝试通过片段合成(路线A)和线性合成(路线B)来合成神经孢苷脂。使用三甲基甲硅烷基三氟甲磺酸酯和N-碘代琥珀酰亚胺/三氟甲磺酸作为促进剂来合成寡糖衍生物。通过路线A无法得到目标四糖,但路线B显示出了潜力:糖苷键(β-D-半乳糖基-(1→6)-β-D-半乳糖基-(1→6)-β-D-半乳糖基)能够立体选择性地形成,从而合成了鞘糖脂2。