Synthesis of Branched Polysaccharides Having Hypoglycaemic Activity

具有降血糖活性的支链多糖的合成

• 批准号: 07651074
• 负责人: HATANAKA Kenichi
• 金额: $ 1.41万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1997
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07651074/
• 关键词: Chemo-Enzymatic Synthesis; Branched Polysaccharide; Hypoglycaemic Activity; D-Xylose; Imidate Method; Curdlan; Natural Polysaccharide; Ring-Opening Polymerization; 分岐多糖; 血統降下作用; 合成多糖; 無水糖; グルコピラナン; 酵素反応; α-D-グルコース

2,4-Di-O-benzyl- (1*6) -alpha-D-glucopyranan which was prepared by cationic ring-opening polymerization of an anhydro glucose derivative was xylosylated at the C-3 position to give xylopyranosyl glucopyranan derivatives. Stereoselectivity of the xylosylation with xylopyranosyl trichloroacetimidate as glycosylating reagent was low. Glucosyl branches were introduced into curdlan ((1*3)-beta-D-glucopyranan) for the purpose of improvement of physical properties of natural polysaccharides. Curdlan was protected by regioselective tritylation at C-6 position, followed by phenylcarbamoylation at C-2 and C-4. Selectively deprotected (detritylated) curdlan was glucosylated to give (1*3) -beta-D-glucopyranan derivative with glucopyranosyl branches. Deprotections of the obtained branched polysaccharide were also attempted. Natural polysaccharide curdlan was then dimethoxytritylated, phenylcarbamoylated, and dedimethoxytritylated in order to prepare a regioselectively protected polysaccharide. The regioselectively protected curdlan was subsequently glucosylated with glucopyranosyl trichloroacetimidate.

将通过脱水葡萄糖衍生物的阳离子开环聚合制备的2，4-二-O-苄基-(1×6)-α-D-吡喃葡萄糖在C-3位进行木糖基化，得到吡喃木糖基吡喃葡萄糖衍生物。以吡喃木糖基三氯乙酰亚胺酯作为糖基化试剂的木糖基化的立体选择性较低。为了改善天然多糖的物理性质，将葡萄糖基支链引入凝胶多糖（(1*3)-β-D-吡喃葡萄糖）中。通过在 C-6 位进行区域选择性三苯甲基化，然后在 C-2 和 C-4 位进行苯基氨基甲酰化来保护凝胶多糖。选择性脱保护（去三苯甲基化）的凝胶多糖被糖基化，得到具有吡喃葡萄糖基支链的（1*3）-β-D-吡喃葡萄糖衍生物。还尝试了所获得的支链多糖的脱保护。然后将天然多糖凝胶多糖进行二甲氧基三苯甲基化、苯基氨基甲酰化和去二甲氧基三苯甲基化，以制备区域选择性保护的多糖。随后用吡喃葡萄糖基三氯乙酰亚胺酯将区域选择性保护的凝胶多糖进行糖基化。

项目成果

K.-I.Kanno, Y.Kobayashi, S.-I.Nishimura, H.Kuzuhara, and K.Hatanaka: "Synthesis of (1→6)-β-Linked N-Acetyl-D-glucosamine Oligosaccharide" Journal of Carbohydrate Chemistry. 14. 481-490 (1995)

K.-I.Kanno、Y.Kobayashi、S.-I.Nishimura、H.Kuzuhara 和 K.Hatanaka：“(1→6)-β-连接 N-乙酰基-D-葡萄糖胺寡糖的合成”杂志碳水化合物化学。14。481-490（1995）

畑中 研一、太田 早苗、門倉 健、粕谷 マリア: "分枝多糖誘導体の精密合成" 高分子論文集. 54. 947-950 (1997)

Kenichi Hatanaka、Sanae Ota、Ken Kadokura、Maria Kasuya：“支链多糖衍生物的精密合成”《高分子科学与技术》杂志 54. 947-950 (1997)。

K.-I.Kanno, Y.Kobayashi, and K.Hatanaka: "Effects of Electron-Withdrawing Groups at C-2 Position of 1,6-Anhydro-Sugars on Their Polymerizabilities" Polym.J.27. 71-77 (1995)

K.-I.Kanno、Y.Kobayashi 和 K.Hatanaka：“1,6-脱水糖 C-2 位吸电子基团对其聚合性的影响”Polym.J.27。

K.-I.Kanno, Y.Kobayashi, S.-I.Nishimura, H.Kuzuhara, and K.Hatanaka: "Synthesis of (1*6) -beta-Linked N-Acetyl-D-glucosamine Oligosaccharide" J.Carbohydr.Chem.14. 481-490 (1995)

K.-I.Kanno、Y.Kobayashi、S.-I.Nishimura、H.Kuzuhara 和 K.Hatanaka：“(1*6)-β-连接 N-乙酰基-D-葡萄糖胺寡糖的合成”J.

Edited by S.Dumitriu: Polysaccharides in Medicine and Biotechnology. MARCEL DEKKER,INC, 3-20 (1996)

S.Dumitriu 编辑：医学和生物技术中的多糖。