Regio-and stereoselective phosphonylation of sugars and its application for anti-cancer and anti-HIV agen

糖的区域和立体选择性磷酸化及其在抗癌和抗HIV药物中的应用

• 批准号: 07555588
• 负责人: YAMAMOTO Iwao
• 金额: $ 2.62万
• 依托单位: Shinshu University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 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-07555588/
• 关键词: phosphenium cation; unsaturated sugar; bioactive; ホスフェニウムイオン; ホスホン化糖; 抗HIV剤; 抗腫瘍剤

Reaction of tri-O-acetylglucal with chloro (diisopropylamino) phosphenium cation gave 1-phosphonylated 2-eno-pyranoside stereo and regioselectivily. After deprotection, endothelin receptor binding accey of the deprotected phosphonylated sugar was investigated, but good results were not obtained.On the other hand, reaction of tri-O-acetylgulucal with diphenylphosphenium cation in dichloromethane, unsaturated sugars having phosphinoyl group on 1-and 3-position was obtained in 51% (1-alpha), 21% (1-beta), and 6% (3-peudaxial), respectively. The stereochemistry of these products were determined by their NOESY spectra. The ozonolysis of 1-phospinoyl-unsaturated sugar in dichloromethane at -78ﾟC gave dialdehyde which cyclyzed in intramolecular aldol-type reaction manner gave franoside in 41% yield. These results will be published elsewhere.

3-O-乙酰基葡萄糖醛与氯(二异丙氨基)膦阳离子反应，得到立体和区域选择性的1-膦酰化的2-烯基吡喃糖苷。另一方面，在二氯甲烷中，三-O-乙酰古鲁糖与二苯基膦阳离子反应，得到1-位和3-位含膦基团的不饱和糖分别为51%(1-α)、21%(1-β)和6%(3-轴)。通过它们的NOESY光谱确定了它们的立体化学结构。1-磷酰基不饱和糖在-78ﾟC的二氯甲烷中臭氧化生成二醛，再以分子内羟醛类型的方式环化，产率为41%。这些结果将在其他地方发表。

项目成果

加坂、藤本、山本、他: "Functionalization of Aminophosphonic Chlorides and Synthesis of Phosphorus Heterocyclic Compounds" Posphorus, Sulfur, and Silicon and related Elements. (印刷中).

Kasaka、Fujimoto、Yamamoto 等人：“氨基膦氯化物的官能化和磷杂环化合物的合成”磷、硫和硅及相关元素（正在出版）。

加坂、藤本、山本、他: "Phosphonylation of Sugar Derivatives using Phosphanylium Cation" Heterocycl. Commun.(印刷中).

Kasaka、Fujimoto、Yamamoto 等人：“使用磷鎓阳离子进行糖衍生物的磷酸化”Heterocycl。