5-bromo-5-deoxy-2,3-O-isopropylidene-D-ribofuranose | 138946-44-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-bromo-5-deoxy-2,3-O-isopropylidene-D-ribofuranose
• 英文别名: (3R,4S,5S)-5-(bromomethyl)-3,4-O-isopropylidenetetrahydrofuran-2,3,4-triol；(3aR,6S,6aS)-6-(bromomethyl)-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-ol
• CAS: 138946-44-8
• 化学式: C₈H₁₃BrO₄
• 分子量: 253.093
• InChiKey: DRVRWXOUKVBSCV-RKEPMNIXSA-N

物化性质

• 沸点：
  339.9±42.0 °C(Predicted)
• 密度：
  1.527±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  47.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5-bromo-5-deoxy-2,3-O-isopropylidene-D-ribofuranose 在 吡啶 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 生成 ethyl 2-[(3aS,4S,6R,6aR)-6-(acetyloxy)-2,2-dimethyltetrahydro-3aH-cyclopenta[d][1,3]dioxol-4-yl]acetate
  参考文献：
  名称：

  New syntheses of carbocycles from carbohydrates. Cyclization of radicals derived from unsaturated halo sugars

  摘要：

  DOI：

  10.1021/jo00204a029
• 作为产物：
  描述：

  2,3-O-异亚丙基-D-核糖酸 gamma-内酯 在 N-溴代丁二酰亚胺(NBS) 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 生成 5-bromo-5-deoxy-2,3-O-isopropylidene-D-ribofuranose
  参考文献：
  名称：

  碘化sa（II）介导的碳水化合物衍生的ω-卤代-α，β-不饱和酯的转化的化学选择性和非对映选择性的研究

  摘要：

  在各种条件下，SmI 2还原了一些碳水化合物衍生的ω-溴-和ω-碘-α，β-不饱和酯。化学选择性随溶剂系统的选择，卤素原子的身份，所用酯的类型，双键的几何形状以及底物的氧化方式而有很大不同。SmI 2介导的反应的立体选择性也受反应参数的影响。

  DOI：

  10.1016/s0040-4020(98)00191-4

文献信息

• A general approach to carbocyclic sugar analogs: preparation of a carbocyclic analog of β-d-fructofuranose
  作者：John J. Gaudino、Craig S. Wilcox

  DOI：10.1016/0008-6215(90)80063-9

  日期：1990.10

  The development and execution of the first examples of a new and general approach to carbocyclic analogs of carbohydrates ("pseudo-sugars") is presented. Complete experimental details for the preparation of the carbocyclic analog of beta-D-fructofuranose 6-phosphate are described for the first time. In the conclusion, the success of the synthetic strategy is analyzed and an approach to retrosynthetic

  介绍了开发和执行碳水化合物（“假糖”）碳环类似物的新通用方法的第一个实例。首次描述了制备β-D-果糖呋喃糖6-磷酸碳环类似物的完整实验细节。最后，分析了合成策略的成功之处，并提出了一种基于“联合合成子”的反合成分析方法。
• Synthesis of Aminocyclitols by Intramolecular Reductive Coupling of Carbohydrate Derived δ- and ε-Functionalized Oxime Ethers Promoted by Tributyltin Hydride or Samarium Diiodide
  作者：José Marco-Contelles、Pilar Gallego、Mercedes Rodríguez-Fernández、Noureddine Khiar、Christine Destabel、Manuel Bernabé、Angeles Martínez-Grau、Jose Luis Chiara

  DOI：10.1021/jo970987w

  日期：1997.10.1

  carbonyl-tethered oxime ethers promoted by samarium diiodide can be performed in a one-pot sequence, following a Swern oxidation step, allowing the direct transformation of hydroxyl-tethered oxime ethers into the corresponding aminocyclitols. Moreover, the resultant O-benzylhydroxylamine products of these cyclizations can be further reduced in situ with excess samarium diiodide, in the presence of water, to the

  据报道，一系列简单或多氧的肟醚经溴化，α，β-不饱和酯，醛或酮基进行了δ-或ε-官能化的分子内还原偶联。还研究了腈系醛的环化。这些还原偶联由氢化三丁基锡或二碘化sa促进。反应在温和的条件下进行，化学收率高，立体选择性高。当应用于衍生自碳水化合物的高度官能化的底物时，该方法可选择性进入具有不同区域和立体化学特征的对映体纯氨基环醇。特别地，由二碘化mar促进的羰基连接的肟醚的还原偶联反应可以在Swern氧化步骤之后按一锅法进行，允许将羟基束缚的肟醚直接转化为相应的氨基环醇。而且，这些环化的所得O-苄基羟胺产物可以在水存在下用过量的二碘化sa原位进一步还原为相应的氨基醇，并具有优异的收率。讨论了这些化合物的一些转化。
• Strategies and tactics for free radical carbocyclization: synthesis of polyfunctionalized cyclopentanoid molecules from carbohydrates
  作者：José Marco-Contelles、Pilar Ruiz、Luis Martínez、Angeles Martínez-Grau

  DOI：10.1016/s0040-4020(01)81837-8

  日期：1993.7

  The tributyltin hydride + azobisisobutyronitrile (AIBN) mediated free radical carbocyclization of precursors 1-9, 48 and 49 is described. The resulting carbocycles have been obtained in moderate yield and good diastereoselectivity. These polyfunctionalized, enantiomerically pure cyclopentane derivatives are useful intermediates for further manipulation.
• Convenient syntheses of orthogonally protected aminocyclopentitols from aldopentoses
  作者：Urban Košak、Martina Hrast、Damijan Knez、Nenad Maraš、Martin Črnugelj、Stanislav Gobec

  DOI：10.1016/j.tetlet.2014.12.008

  日期：2015.1

  Orthogonally protected aminocyclopentitols were synthesized from commercially available aldopentoses using a convenient three-step procedure that does not require protection of the free anomeric hydroxyl group of the starting carbohydrate. The synthesized compounds are important building blocks with potential use in medicinal chemistry and drug discovery. (C) 2014 Elsevier Ltd. All rights reserved.
• An improved synthesis of 5-thio-d-ribose from d-ribono-1,4-lactone
  作者：Jérôme Lalot、Imane Stasik、Gilles Demailly、Daniel Beaupère

  DOI：10.1016/s0008-6215(02)00170-2

  日期：2002.9

  5-Thio-D-ribopyranose was synthesized from D-ribono-1,4-lactone (1) by two approaches: (i) 5-bromo-5-deoxy-D-ribono-1,4-lactone (2) was successively transformed into 5-bromo-5-deoxy, 5-S-acetyl-5-thio or 5-thiocyanato-D-ribofuranose derivatives; appropriate treattncnt then lead to 5-thin-D-ribopyranose (7) in 46-48% overall yield and; (ii) 2 was transformed into the 5-S-acetyl-5-thio-D-ribono-1,4-lactone derivative (11). Reduction and deprotection of 11 afforded 5-thio-D-ribopyranose (7) in 57% overall yield. (C) 2002 Elsevier Science Ltd. All rights reserved.