Development of Novel Glycosylation Reaction Using Odorless Benzenethiols

使用无味苯硫醇开发新型糖基化反应

• 批准号: 20590022
• 负责人: KAJIMOTO Tetsuya
• 金额: $ 3.08万
• 依托单位: Suzuka University of Medical Science
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2008
• 资助国家: 日本
• 起止时间: 2008 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-20590022/
• 关键词: p-オクチルオキシベンゼンチオール; 無臭ベンゼンチオール; グリコシル化反応; 1-チオ-D-グルコサミニド; N-アセチルグルコサミン転移酵素V; NIS; TfOH; PPh3; CCl4; CH3CN試薬系; 非還元末端からの糖鎖合成; p-ドデシルベンゼンチオール; NIS/TsOH; PPh_3/CCl_4/CH_3CN試薬系; p-ドデシルフェニルスルホキシル基; TsOH; PPh_3; CCl_4; CH_3CN試薬系; チオグリコシド; N-アセ

p-Octyloxybenzenethiol (1) was first synthesized as a new odorless benzenethiol. Using 1, 1-(p-octyloxy)phenyl-thio-glycosides (2) were prepared as a new type of glycosyl donors in the glycosylation reaction. After trying the glycosylation reactions under several conditions, it was found that 2 were excellent glycosyl donors in glycosylation reaction activated with N-iodosuccinimide and triflic acid. All the procedure from the preparation of 2 to the glycosylation reaction could be attained completely under conditions where no malodorous stench was generated.Next, another glycosylation reaction was performed using a combination of 2 and 1-(p-octyloxy)phenyl glycosyl sulfoxides (3), which were prepared by the oxidation of 2, as a glycosyl donor and an acceptor, respectively. Promising results were obtained when p-octyloxylphenyl N-phthalimido-D-thio-glucosaminide derivative was activated with NIS and TfOH for the glycosylation of 3 carrying a free hydroxyl group, especially, at the C-6 position. Successive reduction of the resulting disaccharyl sulfoxides with Ph_3P/CBr_4/CH_3CN provided the corresponding thio-glycosides, which could be used as the glycosyl donors in a following glycosylation reaction to afford trisaccharides in good yield. Using the present method, 4-iodo-phenylalkyl ss-D-N-acetylglucosaminyl-(1-2)-ss-D- mannopyranosyl(1-6)-α-D-glucopyranoside (4), which was designed as a monitoring glycoconjugate for the activity of malignant tumor specific N-acetyl-D-glucosaminyltransferase-V.Finally, it is noteworthy that the glycosylation reaction using a combination of 2 and 3, which was developed in the present study, provided a novel and useful synthetic method of oligosaccharides, i. e., the glycosylation reaction from the non-reducing ends.

首先将p-氯辛乙醇（1）合成为新型的苯甲醇生成了臭味。隔离，使用2和1-有希望的结果进行了另一种糖基化，分别通过2的氧化为糖基供体和一个帐户。用NIS和TFOH FOH激活溶剂化的自由羟基，尤其是在带有PH_3P/CBR_4/CH_3CN的dyAccharyl磺氧化物的C-6位置。 。值得注意的是，使用2和3的组合进行糖基化，这是在本研究的寡糖方法中开发的，即来自非还原末端的糖基化反应。

项目成果

N-アセチルグルコサミン転移酵素Vの受容体基質となる三糖誘導体の合成研究

N-乙酰氨基葡萄糖转移酶V受体底物三糖衍生物的合成研究

• 发表时间: 2009
• 作者: 有光健二;木村寛之;小関稔梶本哲也;野出學
• 通讯作者: 野出學

三糖構造を有する糖脂質類似体の合成研究

三糖结构糖脂类似物的合成研究

• 发表时间: 2008
• 作者: 有光健二;木村寛之;小関稔梶本哲也;野出學
• 通讯作者: 野出學

チオグリコシド関連糖供与体の化学選択的グリコシル化反応

硫代糖苷相关糖供体的化学选择性糖基化

• 发表时间: 2009
• 作者: 有光健治;吉増秀礼;梶本哲也;野出學
• 通讯作者: 野出學

チオグリコシド誘導体の組み合わせによる効率的グリコシル化反応の開発

通过硫代糖苷衍生物组合开发有效的糖基化反应

• 发表时间: 2009
• 作者: 有光健治;吉増秀礼;梶本哲也;野出學
• 通讯作者: 野出學

Chemoselective Glycosylation by Using Thioglycoside from Odorless Benzenethiol

使用无味苯硫醇中的硫代糖苷进行化学选择性糖基化

• 发表时间: 2009
• 作者: K.Arimitsu;H.Yoshimasu;T.Kajimoto,M.Node
• 通讯作者: T.Kajimoto,M.Node