Design and Synthesis of Highly Bioactive Sugar-Related Substances

高生物活性糖相关物质的设计与合成

• 批准号: 13470472
• 负责人: IKEGAMI Shiro
• 金额: $ 8.64万
• 依托单位: Teikyo University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-13470472/
• 关键词: Coyolosa; Sugar lactone; L-Iduronic acid; 1-Methylglycoside; Selective glycosylation; Cyclitol; Antidiabetic drug; Voglibose; L-ヘキソース; L-リボース; オルトエステル; スピロ糖

The following research results have been obtained in this research project.1) Coyolosa which is a natural disaccharide having an unusual structure with a 6,6'-ether-linkage was successfully synthesized. In connection with its anti-diabetic activity, 10 kinds of analogs have been synthesized and it was concluded that the reported structure should be revised. A 6,6'-disaccharide formed from two molecules of mannose might be proposed.2) The conversion of sugar lactones to the hydroxamic acid derivatives by the ring opening operation and the recyclization under Mitsunobu conditions gives the corresponding L-sugar. By applying this conversion technique, L-ribose and L-iduronic acid were also synthesized efficiently3) Glycosylation using 1-methylenesugar afforded the corresponding α-D-glycoside stereo-selectively. This method could be applied to synthesize the various types of αglycosides such as α-oligosaccharides exhibiting a potent biological activity.

1)成功地合成了具有6，6‘-醚键结构的天然二糖Coyolosa。针对其抗糖尿病活性，合成了10种类似物，并对其结构进行了修正。由两个甘露糖分子形成的6，6‘-二糖是可能的。2)糖内酯通过开环反应转化为异羟肟酸衍生物，在Mitsunobu条件下再环合得到相应的L糖。利用该转化技术，还合成了L-核糖和L-艾杜糖酸。3)用1-亚甲基葡萄糖进行糖基化反应，立体选择性地得到了相应的α-D-糖苷。该方法可用于合成具有较强生物活性的α糖苷，如α-寡糖。

项目成果

Xiaoliu Li: "Direct Methylenation of Partially Benzyl-protected Sugar Lactones by Dimethyltitinocene"Synlett. 1885-1888 (2001)

李晓柳：“二甲基二茂钛直接甲基化部分苄基保护的糖内酯”Synlett。

Y.M.A.Yamada: "Assembled catalyst of palladium and non-cross-linked amphiphilic polymer ligand for the efficient heterogeneous Heck reaction"Tetrahedron. 60(in press). (2004)

Y.M.A.Yamada：“用于高效非均相 Heck 反应的钯和非交联两亲聚合物配体的组装催化剂”四面体。

Y.M.A.Yamada: "An Assembled Complex of Palladium and Non-Cross-linked Amphiphilic Polymer : a Highly Active and Recyclable Catalyst for The Suzuki-Miyaura Reaction"Org.Lett.. 4(No.20). 3371-3374 (2002)

Y.M.A.Yamada：“钯和非交联两亲聚合物的组装复合物：用于铃木-宫浦反应的高活性且可回收的催化剂”Org.Lett.. 4（No.20）。

Li, Xiaoliu: "Direct Methylation of Partially Benzyl-protected Sugar Lactones by Dimethyltitanocene"SYNLETT. No.12. 1885-1888 (2001)

李小六：“二甲基二茂钛直接甲基化部分苄基保护的糖内酯”SYNLETT。

Y.M.A.Yamada, K.Takeda, H.Takahashi, S.Ikegami: "Assembled Catalyst of Palladium and Non-cross-linked Amphiphilic Polymer Ligand for the Efficient Heterogeneous Heck Reaction"Tetrahedron. 60(in press). (2004)

Y.M.A.Yamada、K.Takeda、H.Takahashi、S.Ikegami：“用于高效多相 Heck 反应的钯和非交联两亲聚合物配体的组装催化剂”四面体。