Reaction and application of perfluoroimidates

全氟亚胺酯的反应及应用

• 批准号: 11672108
• 负责人: NAKAJIMA Noriyuki
• 金额: $ 2.3万
• 依托单位: Toyama Prefectural University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11672108/
• 关键词: perfluoroimidates; trichloroacetimidate; hydration; perfluoronitriles; 3,3-sigmatropic rearrangement; glycosylation; ring opening reaction of epoxide; liposidomycin; エポキシトリフルオロアセトイミダート; エポキシトリクロロアセトイミダート; 立体化学; エポキシ開境反応; 天然物合成; トリフルオロアセトアミド /

We designed and synthesized the perfluoro analogues of benzyl-type, allyl, epoxy and glycosyl imidates in order to improve the chemical properties of trichloroacetimidates. Volatile perfluoronitriles were generated from perfluoroamides with an "activated" dimethyl sulfoxide (DMSO) species at -78 ℃. The key step in perfluoroimidate synthesis was envisioned to be the in situ alcohol addition to perfluoronitriles containing electron-withdrawing substituents on the imidate under dehydration conditions in the presence of DBU.The obtained trifluoroacetimidates were more stable than the trichloro analogue and were easily purified by SiO_2 column chromatography and/or distillation. Obtained MPM- and DMPM- perfluoroimidates could serve as stable protecting reagents for hydroxy functions in place of the trichloroacetimidate with excellent chemical properties and in comparable yields. The 3,3-sigmatropic rearrangement of allylic analogues, acid-catalyzed cyclization of the epoxy analogues and glycosylation of sugar analogues were next studied. Allyl, epoxy and glycosyl trifluoroacetimidates can serve as an exchangeable precursor for the corresponding trichloro analogues.

我们设计并合成了苄基类型，环氧树脂和糖基酰亚胺的类似物，以改善trichloroAcetimidates的化学特性，从而从perfluoronitriles中产生了由“激活的” s at -78 eutiis to perferiis sevision sepione sepione sepione sepriis sepioner。在存在OBU的情况下，在thydration条件下进行了全氟甲硝基的替代品 - 接下来研究了环氧类似物的催化环化和糖类似物的糖基化。

项目成果

Nakajima, N. ; Saito, M. ; Kudo, M. ; Ubukata M.: "Allyl, Epoxy and Glycosyl Perfluoroimidates, One-Pot Preparation and Reaction"Tetrahedron. 58 (in press). (2002)

中岛，N.；

Nakajima, N, Saito, M, Ubukata, M.: "Activated Dimethyl Sulfoxide Dehydration of Amide and Its Application to One-Pot Preparation of Benzyl-type Perfluoroimidates"Tetrahedron. 58(印刷中). (2002)

Nakajima, N, Saito, M, Ubukata, M.：“酰胺的活化二甲基亚砜脱水及其在苄基型全氟亚胺酸酯的一锅制备中的应用”Tetrahedron 58（出版中）。

Nakajima, N., Saito, M., Ubukata, M.: "Activated Dimethyl Sulfoxide Dehydration of Amide and Its Application to One-Pot Preparation of Benzyl-type Perfluoroimidates"Tetrahedron. 58(印刷中). (2002)

Nakajima, N.、Saito, M.、Ubukata, M.：“酰胺的活化二甲基亚砜脱水及其在一锅法制备苄基型全氟亚氨酸酯中的应用”Tetrahedron 58（出版中）。

Nakajima, N., Saito, M., Kudo, M., Ubukata.M.: "Allyl, Epoxy and Glycosyl Perfluoroimidates. One-Pot Preparation and Reaction"Tetrahedron. 58(印刷中). (2002)

Nakajima, N.、Saito, M.、Kudo, M.、Ubukata.M.：“烯丙基、环氧和糖基全氟亚氨酸酯。一锅法制备和反应”Tetrahedron 58（出版中）。

Nakajima, N. ; Saito, M. ; Ubukata, M.: "Activated dimethyl sulfoxide dehydration of amide and its application to one-pot preparation of benzyl-type perfluoroimidates"Tetrahedron. 58 (in press). (2002)

中岛，N.；