权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

Stereochemical Studies on Sialic Acid Derivatives

唾液酸衍生物的立体化学研究

基本信息

批准号：
63470129
负责人：
OGURA Haruo
金额：
$ 3.26万
依托单位：
Kitasato University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (B)
财政年份：
1988
资助国家：
日本
起止时间：
1988 至 1990
项目状态：
已结题

项目摘要

1. Synthesis of KDNNeu5Ac was obtained from edible bird's nest, and KDN was synthesized from D-mannose and oxalacetic acid. Because the yield of thermal rearrangement of Neu5Ac nitroso derivative to KDN was very low.2. Glycosilation of Neu5AcSyntheses of various kind of Neu5Ac derivatives were carried out from (Neu4, 5, 7, 8, 9-Ac_52betaCl1Me). From the chloride, sialosyl-lactose, -cholesterol, -monosaccharide, and -disaccharide nucleoside analogs were synthesized under the Koenigs-Knorr reaction conditions.3. Glycosylation of KDNBenzyl (methyl 3-deoxy-D-glycero-alpha-D-galacto-2-nonulopyranosid) onate and sodium 2- (5-cholestenyl-3beta-oxy) -3-deoxy-D-glycero-alpha-and-beta-D-galacto-2-nonulopyranosonate were synthesized under the Koenigs-Knorrection. Benzyl (4, 5, 7, 8, 9-penta-0-acetyl-3-deoxy-D-glycero-beta-D-galacto-2-nonulopyranosyl bromid) onate was used as a glycosyl donor.4. Glycosylation with Williamson ReactionWilliamson reaction was applied to ferrulic acid, estradiol, umberiferon, and mitomycin derivatives with Neu5Ac chloride to yield alpha-glycosides in good yields. Mitomycin derivatives were prepared, by a similar method.5. Confirmation of stereochemistry(1) NMR and CD spectral method Their structure and stereochemistry were determined by means of NMR and CD spectral analyses.(2) Hydrolysis method Hydrolysis of alpha-and beta-methyl neuraminate were proved. alpha-Anomer was hydrolyzed in 1 hr, while, beta-anomer was stable after 5 hr. Similarly, alpha- (2->6) sialosyllactose was hydrolyzed completely at 80ﾟC in 1 hour. In contrast, the beta-anomer was stable at 80^ﾟC for 5 hr.

1.以燕窝为原料合成KDNNeu 5Ac，以D-甘露糖和N-乙酸为原料合成KDN。由于Neu 5Ac亚硝基衍生物热重排生成KDN的产率很低. Neu 5Ac的糖基化从（Neu 4，5，7，8，9-Ac_52 β Cl 1 Me）进行各种Neu 5Ac衍生物的合成。以氯化物为原料，在Koenigs-Knorr反应条件下，合成了唾液酸-乳糖、-胆固醇、-单糖和-二糖核苷类似物. KDN的糖基化在Koenigs-Knorrection下合成了（3-脱氧-D-甘油-α-D-半乳糖-2-壬糖基）奥纳特和2-（5-辛烯基-3 β-氧）-3-脱氧-D-甘油-α-和-β-D-半乳糖-2-壬糖基吡喃糖酸钠。苄基（4，5，7，8，9-五-O-乙酰基-3-脱氧-D-甘油基-β-D-半乳糖基-2-吡喃壬糖基溴）奥纳特用作糖基供体。用威廉姆森反应进行糖基化将威廉姆森反应应用于亚铁酸、雌二醇、伞形酮和丝裂霉素衍生物与Neu 5 Ac氯化物的反应，以高产率产生α-糖苷。丝裂霉素衍生物的制备，通过类似的方法.立体化学的确证（1）NMR和CD光谱法通过NMR和CD光谱分析确定了它们的结构和立体化学。(2)水解方法证明了α-和β-神经氨酸甲酯的水解。α-端基异构体在1小时内水解，而β-端基异构体在5小时后稳定。同样，α-（2->6）唾液酸乳糖在80 ℃下1小时内完全水解。相比之下，β-端基异构体在80 ° C下稳定5小时。

项目成果

期刊论文数量（98）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Naokazu Sugiyama, Kei Sugai, Noriyuki Yamada, Motoaki Goto, Chieko Ban, Kimio Furuhata, Hiroaki Takayanagi, and Haruo Ogura: ""Formation of 1, 7-Lactone Derivatives by Direct Acylation of N-Acetylneuraminic Acid"" Chem. Pharm. Bull.36. 1147-1152 (1988)

Naokazu Sugiyama、Kei Sugai、Noriyuki Yamada、Motoaki Goto、Chieko Ban、Kimio Furuhata、Hiroaki Takayanagi 和 Haruo Ogura：“通过 N-乙酰神经氨酸的直接酰化形成 1, 7-内酯衍生物”Chem。