2,3-O-isopropylidene-5-O-methyl-β-D-ribofuranosyl fluoride | 149002-58-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,3-O-isopropylidene-5-O-methyl-β-D-ribofuranosyl fluoride
• 英文别名: 5-O-methyl-2,3-O-isopropylidene-β-D-ribofuranosyl fluoride；(3aR,4S,6R,6aR)-4-fluoro-6-(methoxymethyl)-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxole
• CAS: 149002-58-4
• 化学式: C₉H₁₅FO₄
• 分子量: 206.214
• InChiKey: AFXUQSCASSWZQP-WCTZXXKLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,3-O-isopropylidene-5-O-methyl-β-D-ribofuranosyl fluoride 、 O,O-二(三甲基甲硅烷基)胸苷 在 silicon tetrafluoride 作用下， 以 乙腈 为溶剂， 反应 3.5h， 生成 5'-deoxy-2',3'-O-isopropylidene-5'-O-methyl0ribothymidine
  参考文献：
  名称：

  Some intramolecular rearrangements when pentofuranoses are treated with diethylaminosulphur trifluoride (DAST)

  摘要：

  Treatment of methyl 2,3-O-isopropylidene-beta-D-ribofuranoside with DAST gave a good yield of 2,3-O-isopropylidene-5-0-methyl-beta-D-ribofuranosyl fluoride in which the methoxy group had migrated from C-1 --> C-5 and been replaced with retention of configuration by fluorine. The corresponding aldehyde when treated under similar conditions underwent a similar migration to give 5-deoxy-5-fluoro-2,3-O-isopropylidene-5-O-methyl-beta-D-ribofuranosyl fluoride. A similar migration occurred with methyl 2',3'-di-O-acetyl-beta-D-ribofuranoside and with acetyl 2,3-O-isopropylidene-D-ribofuranose but not with 1,2,3-tri-O-acetyl-D-ribofuranose. Thus the migration depends upon the migratory aptitude of the substituent at C-1 and the conformation of the furanose ring. Two ribofuranosyl fluorides were used as starting materials from which to make nucleosides by the method of Noyori and Hayoshi.

  DOI：

  10.1016/s0022-1139(00)80038-x
• 作为产物：
  描述：

  甲基-2,3-O-异亚丙基-beta-D-呋喃核糖苷 在 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以55%的产率得到2,3-O-isopropylidene-5-O-methyl-β-D-ribofuranosyl fluoride
  参考文献：
  名称：

  Some intramolecular rearrangements when pentofuranoses are treated with diethylaminosulphur trifluoride (DAST)

  摘要：

  Treatment of methyl 2,3-O-isopropylidene-beta-D-ribofuranoside with DAST gave a good yield of 2,3-O-isopropylidene-5-0-methyl-beta-D-ribofuranosyl fluoride in which the methoxy group had migrated from C-1 --> C-5 and been replaced with retention of configuration by fluorine. The corresponding aldehyde when treated under similar conditions underwent a similar migration to give 5-deoxy-5-fluoro-2,3-O-isopropylidene-5-O-methyl-beta-D-ribofuranosyl fluoride. A similar migration occurred with methyl 2',3'-di-O-acetyl-beta-D-ribofuranoside and with acetyl 2,3-O-isopropylidene-D-ribofuranose but not with 1,2,3-tri-O-acetyl-D-ribofuranose. Thus the migration depends upon the migratory aptitude of the substituent at C-1 and the conformation of the furanose ring. Two ribofuranosyl fluorides were used as starting materials from which to make nucleosides by the method of Noyori and Hayoshi.

  DOI：

  10.1016/s0022-1139(00)80038-x

文献信息

• Method of fluorination
  申请人：Hara Shoji

  公开号：US20060014972A1

  公开（公告）日：2006-01-19

  A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200° C. where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

  一种氟化方法，包括通过热力学或微波辐射或波长在微波区域附近的电磁波与一种通式为(I)的氟化试剂反应，反应单糖，低聚糖，多糖，由这些糖与蛋白质和脂质结合形成的复合糖和具有多元醇，醛，酮和多元醇的酸以及这些化合物的衍生物和缩聚物。根据该方法，可以在150到200°C的温度范围内安全地进行选择性的氟化反应，而在传统方法中难以进行。上述方法包括使用微波或波长在微波区域附近的电磁波辐射，可应用于除糖类以外的基质。当HF和碱组成的复合物在微波辐射下反应时，难以在传统方法中进行的特定位置的氟化反应高度选择性，高效地在短时间内安全进行。
• METHOD OF FLUORINATION
  申请人：MITSUBISHI GAS CHEMICAL COMPANY, INC.

  公开号：EP1568703A1

  公开（公告）日：2005-08-31

  A method of fluorination comprising reacting monosaccharides, oligosaccharides, polysaccharides, composite saccharides formed by bonding of these saccharides with proteins and lipids and saccharides having polyalcohols, aldehydes, ketones and acids of the polyalcohols, and derivatives and condensates of these compounds with a fluorinating agent represented by general formula (I) thermally or under irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region. In accordance with the method, the fluorination at a selected position can be conducted safely at a temperature in the range of 150 to 200°C where the reaction is difficult in accordance with conventional methods. The above method comprising the irradiation with microwave or an electromagnetic wave having a wavelength around the microwave region can be applied to substrates other than saccharides. When a complex compound comprising HF and a base is reacted under irradiation with microwave, fluorination at a specific position which is difficult in accordance with conventional methods proceeds highly selectively, efficiently in a short time and safely.

  一种氟化方法，包括使单糖、低聚糖、多糖、这些糖与蛋白质和脂类结合形成的复合糖、具有多元醇、多元醇的醛、酮和酸的糖、以及这些化合物的衍生物和缩合物与通式(I)代表的氟化剂进行热反应或在微波或波长在微波区域附近的电磁波照射下进行反应。根据该方法，可在 150 至 200°C 的温度范围内安全地进行所选位置的氟化反应，而在此温度范围内，根据传统方法很难进行反应。上述方法包括用微波或波长在微波区域附近的电磁波进行辐照，可用于糖类以外的基质。在微波辐照下反应由氟化氢和碱组成的复杂化合物时，在传统方法难以进行的特定位置上的氟化反应可在短时间内高效、安全地进行，且选择性高。
• METHOD OF FLUORINATION BY MICROWAVES
  申请人：Mitsubishi Gas Chemical Company, Inc.

  公开号：EP2189466A2

  公开（公告）日：2010-05-26

  A method of fluorination which comprises fluorinating a substrate by bringing the substrate and a fluorinating agent into reaction with each other under irradiation with at least one of microwave and electromagnetic wave having a wavelength around a microwave region; wherein the substrate is selected from the group consisting of monohydroxy alcohol; polyol having a plurality of hydroxyl groups; thiol; a compound having a carbonyl group or carboxyl group; an aromatic compound exhibiting an increased nucleophilicity due to the presence of an electron-attracting group; aromatic diazonium salt; oligosaccharide and polysaccharide; hydrocarbon having a cage shape; and epoxide; and the fluorinating agent is represented by general formula (I): wherein Y represents nitrogen atom or phosphorus atom, R0, R1 and R2 represent hydrogen atom or an alkyl or aryl group which may have substituents, the atom and the groups represented by R0, R1 and R2 may be the same with or different from each other, and two or three of the groups represented by R0, R1, and R2 may be bonded to each other to form a ring.

  一种氟化方法，包括在微波和波长在微波区域附近的电磁波中的至少一种的辐照下，使基质和氟化剂相互反应，从而使基质氟化；其中基质选自由单羟基醇组成的组；具有多个羟基的多元醇；硫醇；具有羰基或羧基的化合物；由于存在引电子基团而亲核 性增强的芳香族化合物；芳香族重氮盐；寡糖和多糖；具有笼形的碳氢化合物；以及环氧 物；氟化剂由通式(I)表示： 其中 Y 代表氮原子或磷原子，R0、R1 和 R2 代表氢原子或可带有取代基的烷基或芳基，R0、R1 和 R2 所代表的原子和基团可以彼此相同或不同，R0、R1 和 R2 所代表的两个或三个基团可以彼此键合形成环。
• Method of fluorination by microwaves
  申请人：Mitsubishi Gas Chemical Company, Inc.

  公开号：EP2189467A2

  公开（公告）日：2010-05-26

  A method of fluorination which comprises fluorinating a substrate by bringing the substrate and a complex compound comprising HF and a base into reaction with each other under irradiation with at least one of microwave and electromagnetic wave having a wavelength around a microwave region; wherein the substrate is selected from the group consisting of a compound having hydrogen atom activated by a substituent at the α position, the β-position or the γ-position, a silyl ether compound, a compound having an unsaturated group, hydroxyl group, halogeno group, amino group, diazo group, triazeno group or isocyano group as a functional group, a saccharide and a cyclic compound having a three-membered or greater ring which may have a heteroatom.

  一种氟化方法，包括在微波和波长在微波区域附近的电磁波中的至少一种波长的辐照下，使基质和由氢氟酸和碱组成的复合物相互反应，从而使基质氟化； 其中基质选自由下列组成的化合物：在α位、β位或γ位有被取代基活化的氢原子的化合物；硅烷基醚化合物；具有不饱和基团、羟基、卤基、氨基、重氮基团、三氮基团或异氰基作为官能团的化合物；糖类和具有三元或三元以上环且可能具有杂原子的环状化合物。
• Deoxyfluorination of alcohols using N,N-diethyl-α,α-difluoro-(m-methylbenzyl)amine
  作者：Shingo Kobayashi、Atushi Yoneda、Tsuyoshi Fukuhara、Shoji Hara

  DOI：10.1016/j.tet.2004.05.089

  日期：2004.8

  Deoxyfluorination of alcohols was carried out using N,N-diethyl-alpha,alpha-difluoro-(m-methylbenzyl)amine (DFMBA). Primary alcohols were effectively converted to fluorides under microwave irradiation or conventional heating. Deoxyfluorination of an anomeric hydroxy group in sugars by DFMBA proceeded at below room temperature and glycosyl fluorides could be obtained in good yields. The deoxyfluorination reaction chemoselectively proceeded and various protecting groups on the sugar can survive under the reaction conditions. (C) 2004 Elsevier Ltd. All rights reserved.