DEVELOPMENT OF THE NEW ORGANIC REACTION BY USING NEW LEWIS ACID, BF_2(Otf)

使用新路易斯酸 BF_2(Otf) 开发新的有机反应

• 批准号: 13672227
• 负责人: HORITA Kiyoshi
• 金额: $ 2.18万
• 依托单位: FACULTY OF PHARMACEUTICAL SCIENCES HEALTH SCIENCES UNIVERSITY OF HOKKAIDO
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13672227/
• 关键词: BF_3-Oet_2; Me_3SiOTf; Lewis acid; C-allylglycosidation; BF_2(Otf); ルイス酸; トリメチルシリルトソフラート; 三フッ化ホウ素エーテル錯体; C-アリルグリコシル化; アリル-C-グリコシル化

We found a new Lewis acid which were easily generated from BF_3-Oet_2 complex and Me_3SiOTf in 1:1 ratio, as the most general and popular Lewis acid in organic synthesis, in acetonitrile. Structure of the newly generated Lewis acid were determined as BF_2(Otf) by measurement of ^1H-NMR, ^<19>F-NMR abd ^<11>B-NMR. The most important information from those NMR measurement results was detection of the Me_3SiF. Generation of the molecular spices indicates that transmetalation reaction take place quickly between BF_3-Oet_2 complex and Me_3SiOTf in acetonitrile.This newly developed Lewis acid, as BF_2(Otf), was examined toward some Lewis acid mediated organic reactions. It found that this new Lewis acid was very useful. Especially, highly stereocontrolled C-allylglycosidation reaction efficiently took place toward some kinds of methyl pyranose derivatives, idose, glucose and galactose, with free hydroxyl groups (no protecting groups)

我们发现了一种新的刘易斯酸，它是有机合成中最常用的刘易斯酸，它是由BF_3-Oet_2配合物和Me_3SiOTf按1：1的比例在乙腈中生成的。新生成的刘易斯酸经~ 1H-NMR、~ 1F-NMR和~ 1B-NMR测定，确定其结构为BF_2（OTf）<19><11>。这些NMR测量结果中最重要的信息是Me_3SiF的检测。分子香料的生成表明，在乙腈中，BF_3-Oet_2配合物与Me_3SiOTf之间发生了快速的金属转移反应，并将这种新的刘易斯酸命名为BF_2（OTF），用于刘易斯酸介导的有机反应。发现这种新的刘易斯酸非常有用。特别是对某些具有自由羟基（无保护基）的甲基吡喃糖衍生物，艾杜糖，葡萄糖和半乳糖，都能有效地进行高度立体控制的C-烯丙基糖苷化反应

项目成果

Horita, K., Noguchi, Y., Matsunaga, M., Uchida, M., Shimizu, K., Kouno, T., Tsunoo, A., Nishibe, S: "Anti-arrhythmia Constituent in Herba Leonuri"Natural Medicines. 56(5). 212-214 (2002)

Horita, K.、Noguchi, Y.、Matsunaga, M.、Uchida, M.、Shimizu, K.、Kouno, T.、Tsunoo, A.、Nishibe, S：“益母草中的抗心律失常成分”天然药物

Kiyoshi Horita: "Cytotoxic constituents in the holdfast of cultivated Laminaria japonica"Fishers Sciences. (in press). (2003)

Kiyoshi Horita：“栽培海带固着物中的细胞毒性成分”渔民科学。

Horita, K., Noguchi, Y., Matsunaga, M., Uchida, M., Shimizu, K., Kouno, T., Tsunoo, A., Nishibe, S.: "Anti-arrhythmia Constituent in Herba Leonuri"Natural Medicines. 56(5). 212-214 (2002)

Horita, K.、Noguchi, Y.、Matsunaga, M.、Uchida, M.、Shimizu, K.、Kouno, T.、Tsunoo, A.、Nishibe, S.：“益母草中的抗心律失常成分”天然

Nishizawa, M., Takahashi, N., Shimozawa, K, Aoyama, T., Satoh, N., Jimbou, K., Noguchi, Y., Horita, K., Bandou, H., Yamagishi, T.: "Cytotoxic constituents in the holdfast of cultivated Laminaria japonica"Fisheries Science. (in press). (2003)

西泽，M.，高桥，N.，下泽，K，青山，T.，佐藤，N.，Jimbou，K.，野口，Y.，堀田，K.，班杜，H.，山岸，T.：“

Horita, K., Ohta, N., Takahashi, N., Noguchi: "Research on Anti-tumor Active Site of Marine Source Compound, Halichondrin B Inhibitory Activity of C37-C54 Part Derivatives toward the Breast and Esophagus Cancer Cell Lines"Bull. Marine Biomed. Inst., Sappo

Horita, K.、Ohta, N.、Takahashi, N.、Noguchi：“海洋源化合物的抗肿瘤活性位点研究，软海绵素 B C37-C54 部分衍生物对乳腺癌和食道癌细胞系的抑制活性”公牛