2,3,5-tri-O-benzyl-D-arabinofuranosyl fluoride | 94898-52-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2,3,5-tri-O-benzyl-D-arabinofuranosyl fluoride
• 英文别名: (2R,3S,4R,5R)-2-fluoro-3,4-bis(phenylmethoxy)-5-(phenylmethoxymethyl)oxolane
• CAS: 94898-52-9
• 化学式: C₂₆H₂₇FO₄
• 分子量: 422.496
• InChiKey: XRTVLEDCQXWQBB-XPGKHFPBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.6
• 重原子数：
  31
• 可旋转键数：
  10
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.31
• 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：

  2,3,5-tri-O-benzyl-D-arabinofuranosyl fluoride 在 palladium dihydroxide 氢气 、 tin(ll) chloride 作用下， 以 甲醇 、 乙醚 为溶剂， 生成 sucrose
  参考文献：
  名称：

  Preferred Conformation of C-Glycosides. 13. A Comparison of the Conformational Behavior of Several C-, N-, and O-Furanosides

  摘要：

  A qualitative comparison of C-furanosides, derived from arabinose and 2-deoxyribose, with the naturally occurring O- and N-furanosides was performed using solution H-1 NMR spectroscopy and X-ray crystallography. The ring conformations of beta- and alpha-C-arabino and beta- and alpha-C-2-deoxyribofuranosides tend to possess equatorial anomeric C-C bonds, in contrast to the O-furanosides, which have ring conformations stabilized by axial anomeric C-O bonds due to a stereoelectronic effect. Installation of a quaternary anomeric center in C-furanosides introduces unfavorable 1,3-diaxial-like steric interactions, which can shift the ring conformational equilibrium in such a manner that the C-furanoside becomes more similar to the O-furanoside. The solid-state conformation of the C-nucleoside beta-arabinosyl pseudouridine was shown to be virtually identical to N-nucleoside beta-arabinosyluridine. In solution, however, the ring conformation of this N-furanoside, and its 2-deoxy analog, is intermediate to the corresponding oxygen- and carbon-derived entries. When compared to C-pyranosides, C-furanosides seem to have anomeric linkages prone to increased exo-anomeric conformational averaging. A quaternary furanosyl anomeric center such as in O-sucrose (1) and C-sucrose (2) appears to provide further flexibility at this anomeric linkage. Evidence is provided which suggests the flexible nature of sucrose arises at the fructofuranosyl linkage, as the glucopyranosyl linkage in this compound is conformationally well-defined in the exo-anomeric sense. The analysis of the preferred syn/anti base conformation in C-nucleosides can be complicated by a stronger equatorial base preference.

  DOI：

  10.1021/jo00101a022
• 作为产物：
  描述：

  2,3,5-tri-O-benzyl-D-arabinose 在 二乙胺基三氟化硫 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以68.254%的产率得到
  参考文献：
  名称：

  合成与A型Prymnesin毒素有关的甘油糖苷

  摘要：

  化学合成了代表糖基化鱼腥毒素各种片段的一组糖基化甘油衍生物，称为酪蛋白。甘油用于代表胰泌乳素主链的小片段，并在2°位置被糖基化，据报道糖存在于胰泌乳素毒素上。利用邻近基团的参与来合成1，2-反式-糖苷。SnCl2促进呋喃糖基氟糖基化得到1,2-顺式呋喃糖苷具有适度的立体控制，而TMSOTf促进与呋喃糖基亚氨酸盐的糖基化得到具有良好立体控制的1,2-顺式呋喃糖苷。还描述了用α-α-阿拉伯糖吡喃糖和α-β-呋喃核糖糖基化的两个新的较大的Prymnesin-1甘油基二糖苷片段。由于在该区域的胚乳主链的立体化学是不确定的，因此合成了2R-和2S-甘油异构体。通过比较NOESY NMR和计算模型来区分分离的非对映异构体。

  DOI：

  10.1016/j.carres.2018.04.008

文献信息

• THE SYNTHESIS OF GLYCOSYL FLUORIDES USING PYRIDINIUM POLY(HYDROGEN FLUORIDE)
  作者：Walter A. Szarek、Grzegorz Grynkiewicz、Bogdan Doboszewski、George W. Hay

  DOI：10.1246/cl.1984.1751

  日期：1984.10.5

  Partially protected monosaccharides, having the anomeric hydroxyl group underivatized, react with poly(hydrogen fluoride) to yield the corresponding glycosyl fluorides.

  部分保护的单糖，异头羟基未衍生，与聚（氟化氢）反应生成相应的糖基氟化物。
• Bis(2-methoxyethyl)aminosulfur trifluoride: a new broad-spectrum deoxofluorinating agent with enhanced thermal stability
  作者：Gauri S. Lal、Guido P. Pez、Reno J. Pesaresi、Frank M. Prozonic

  DOI：10.1039/a808517j

  日期：——

  Bis(2-methoxyethyl)aminosulfur trifluoride (Deoxo-FluorTM) is effective for the conversion of alcohols to alkyl fluorides, aldehydes/ketones to the corresponding gem-difluorides and also for the transformation of carboxylic acids to their trifluoromethyl derivatives; it is a less thermally sensitive, broader-spectrum alternative to the traditional dialkylaminosulfur trifluoride (DAST) deoxofluorination reagents.

  双(2-甲氧乙基)氨基硫三氟化物（Deoxo-FluorTM）在将醇转化为烷基氟化物、将醛/酮转化为相应的双氟化物，以及将羧酸转化为其三氟甲基衍生物方面有效；它是传统的二烷基氨基硫三氟化物（DAST）脱氧氟化试剂的一个热敏感性较低、适用范围更广的替代品。
• Direct <i>C</i>-Glycosylation of Organotrifluoroborates with Glycosyl Fluorides and Its Application to the Total Synthesis of (+)-Varitriol
  作者：Jing Zeng、Seenuvasan Vedachalam、Shaohua Xiang、Xue-Wei Liu

  DOI：10.1021/ol102473k

  日期：2011.1.7

  C-glycosides via BF3·Et2O promoted coupling of organotrifluoroborates and glycosyl fluorides is reported. The application of this method was further demonstrated by the concise and efficient total synthesis of (+)-varitriol in only seven steps.

  据报道，通过BF 3 ·Et 2 O促进了有机三氟硼酸酯和糖基氟化物的偶联，采用了温和，立体选择性和快速的方法访问炔基和烯基C-糖苷。该方法的应用通过仅七个步骤的简明有效的全合成（+）-varitriol进一步得到了证明。
• Condensation of 1-Fluorofuranoses and Silylated Nucleobases Catalyzed by Tetrafluorosilane
  作者：Ryoji Noyori、Masahiko Hayashi

  DOI：10.1246/cl.1987.57

  日期：1987.1.5

  The title reaction provides a generally useful tool for nucleoside synthesis. The stereoselectivities are highly influenced by the fluoride substrates, and steric course of the reaction of O-benzylated ribofuranosyl fluoride is solvent dependent.

  标题反应为核苷合成提供了一个普遍有用的工具。立体选择性受氟化物底物的影响很大，并且 O-苄基化呋喃核糖基氟反应的空间过程是溶剂依赖性的。
• 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.