3,5-diazido-3,5-dideoxy-1,2-O-isopropylidene-α-D-pentafuranose | 75252-14-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,5-diazido-3,5-dideoxy-1,2-O-isopropylidene-α-D-pentafuranose
• 英文别名: 1,2-O-isopropylidene-3,5-diazido-3,5-dideoxy-α-D-ribofuranose；1,2-O-isopropylidene-3,5-dideoxy-3,5-diazido-α-D-xylofuranose；3,5-diazido-3,5-dideoxy-1,2-O-isopropylidene-α-D-ribofuranose；3,5-dideoxy-3,5-diazido-1,2-O-isopropylidene-ribofuranose；(3aR,5R,6R,6aR)-6-azido-5-(azidomethyl)-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxole
• CAS: 75252-14-1
• 化学式: C₈H₁₂N₆O₃
• 分子量: 240.222
• InChiKey: WTFICEWCYTYABE-DBRKOABJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  56.4
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  3,5-diazido-3,5-dideoxy-1,2-O-isopropylidene-α-D-pentafuranose 在 palladium on activated charcoal 、 三乙酰氧基硼氢化钠 作用下， 以 乙醇 、 1,2-二氯乙烷 为溶剂， 反应 24.0h， 生成 3,5-aminodideoxy-3-N-(methyl(N-methylimidazol-2-yl))-5-N,N-di(methyl(N-methylimidazol-2-yl))-1,2-Oisopropylidene-α-D-ribofuranose
  参考文献：
  名称：

  通过在具有稳定 CuI 的累积弱力的糖配体中进行钩环紧固的 Entasis

  摘要：

  Vallee 和 Williams 提出了通过约束配位球几何来可能控制金属离子特性的想法，并提出了 entasis 的概念，这通常被认为与金属生物分子有关。然而，控制金属中心几何形状的相互作用往往难以捉摸。在这项研究中，以糖支架为中心的几何约束糖配体对铜离子（Cu(II) 或 Cu(I)）的配位特性与构建在不受约束的烷基链上的类似配体的配位特性进行了比较。与开链类似物相比，以糖为中心的配体对 Cu(II) 配位的预组织程度更高，并且对 Cu(I) 氧化还原状态具有不寻常的额外稳定性。这种对 Cu(I) 的偏好被认为是由于几何约束有利于优化糖配体的折叠，从而最大限度地减少空间排斥。换句话说，Cu(I) d(10) 物种通过价壳电子对排斥 (VSEPR) 稳定。这一想法被理论非共价相互作用 (NCI) 分析合理化。弱力的累积效应显示出在钩环紧固件中产生有效的扣环，并且双配体内的精细结构特征减少了

  DOI：

  10.1021/ja510259p
• 作为产物：
  描述：

  1,2:3,5-双-O-异亚丙基-alpha-D-呋喃木糖 在 吡啶 、 盐酸 、 叠氮化锂 作用下， 以 N-甲基吡咯烷酮 为溶剂， 反应 8.5h， 生成 3,5-diazido-3,5-dideoxy-1,2-O-isopropylidene-α-D-pentafuranose
  参考文献：
  名称：

  Synthesis of Different 3,5‐Diazidofuranoses: A New and General Synthesis Pathway

  摘要：

  Diamino- and diazidofuranoses represent useful precursors, for example, for the synthesis of substituted nucleosides and metal complexes, respectively. Known procedures for their synthesis lack the availability of cheap starting materials, adequate yields, and the access to all possible diastereomeres. Therefore, 3,5-diazido-3,5-dideoxy- and - 2,3,5- trideoxyfuranoses both with ribo- and xylo- configuration were prepared using different approaches.

  DOI：

  10.1080/07328300701540175

文献信息

• Synthesis and Properties of New Nucleotide Analogues Possessing Squaramide Moieties as New Phosphate Isosters
  作者：Kohji Seio、Takuhei Miyashita、Kousuke Sato、Mitsuo Sekine

  DOI：10.1002/ejoc.200500520

  日期：2005.12

  condensation of 5′- or 3′-aminonucleosides with dimethyl squarate, whilst the selective removal of the methyl group was effectively accomplished by treatment with sodium bromide. In addition, we also synthesized 3′,5′-cyclic nucleotide analogues from the 3′,5′-diazidonucleoside derivatives. NMR analysis revealed that their ribose puckering was of an N-type form, identical to that in cAMP and cGMP. Because

  合成了结合独特方酸酰胺结构的 2'-脱氧核苷酸和核糖核苷酸的新类似物。由于该部分的强酸性（pKa = 2.3），这些核苷酸类似物以单阴离子形式存在，在生理条件下可以被视为5'-核苷酸的电子等排体。核苷酸类似物的合成是通过 5'-或 3'-氨基核苷与方酸二甲酯的缩合来实现的，而甲基的选择性去除则是通过用溴化钠处理来有效实现的。此外，我们还从 3',5'-二叠氮核苷衍生物合成了 3',5'-环核苷酸类似物。核磁共振分析表明，它们的核糖起皱是一种 N 型形式，与 cAMP 和 cGMP 中的相同。由于独特的结构、电子、和方酸酰胺型核苷酸类似物的构象特性，这些类似物作为潜在的生物活性化合物，如抗病毒和抗癌剂，应该是非常有趣的。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)
• Mitsunobu Transformations of 1,2-O-Isopropylidene-α-D-pentofuranoses Mediated by Zinc Salts
  作者：Jitka Moravcová、Lucie Špilová、Jindra Čapková、Florence Chery、Patrick Rollin

  DOI：10.1135/cccc20001745

  日期：——

  A one-pot regioselective heterofunctionalization of 1,2-O-isopropylidene-α-D-xylofuranose (1) and 1,2-O-isopropylidene-α-D-ribofuranose (2) with zinc azide, zinc thiocyanate or zinc N,N-dimethyldithiocarbamate via the Mitsunobu reaction has been performed. With 2, the reaction gave selectively the desired products substituted at C-5 in good isolated yields (60-65%). However, application of the same reaction conditions to 1 led to the predominant formation of a cyclic 3,5-anhydro derivative. In contrast, the reaction of hydrazoic acid with 1 afforded 5-azido-5-deoxy-1,2-O-isopropylidene-α-D-xylofuranose besides formerly unknown 5-azido-3,5-dideoxy-1,2-O-isopropylidene-α-D-glycero-pent-3-enofuranose and 3,5-diazido- 3,5-dideoxy-1,2-O-isopropylidene-α-D-ribofuranose; the yields depended on the reaction time and the molar ratio of reagents.

  一锅法的选择性杂功能化反应已经用锌叠氮化物、硫氰酸锌或锌N，N-二甲基二硫代氨基甲酸酯通过Mitsunobu反应成功地对1,2-O-异丙基-α-D-木糖呋喃糖（1）和1,2-O-异丙基-α-D-核糖呋喃糖（2）进行了。对于2，反应在C-5位置选择性地给出了所需产物，且收率良好（60-65%）。然而，将相同的反应条件应用于1，则主要形成了环状3,5-缩水衍生物。相反，将叠氮酸与1反应得到了5-叠氮基-5-去氧-1,2-O-异丙基-α-D-木糖呋喃糖，以及前所未知的5-叠氮基-3,5-二去氧-1,2-O-异丙基-α-D-甘油-3-烯酮呋喃糖和3,5-二叠氮基-3,5-二去氧-1,2-O-异丙基-α-D-核糖呋喃糖；产率取决于反应时间和试剂的摩尔比。
• Sugar-Based Diphosphoroamidite as a Promising New Class of Ligands in Pd-Catalyzed Asymmetric Allylic Alkylation Reactions
  作者：Eva Raluy、Montserrat Diéguez、Oscar Pàmies

  DOI：10.1021/jo062311j

  日期：2007.4.1

  available modular diphosphoroamidite ligands from d-xylose for Pd-catalyzed asymmetric allylic alkylation reactions. This constitutes the first example of diphosphoroamidite ligands applied to this process. Good-to-excellent activities (TOFs up to 850 mol substrate × (mol Pd × h)-1) and enantioselectivities (ee's up to 95%) have been obtained for several substrates with different electronic and steric properties

  我们已经设计了一个新的家族，它由d-木糖构成的易于使用的模块化二磷酰胺基配体，用于Pd催化的不对称烯丙基烷基化反应。这构成了用于该方法的二磷酰胺基配体的第一个实例。对于具有不同电子和空间特性的几种底物，已经获得了优良的活性（TOF高达850 mol底物×（mol Pd×h）-1）和对映选择性（ee高达95％）。结果表明，催化性能受到取代基和配体联芳基部分的轴向手性的高度影响。我们还讨论了Pd-π-烯丙基中间体的合成和表征，以使用这些催化系统更深入地了解对映选择性的起源。
• Sugars to Control Ligand Shape in Metal Complexes: Conformationally Constrained Glycoligands with a Predetermination of Stereochemistry and a Structural Control
  作者：Ludivine Garcia、Stéphane Maisonneuve、Juan Xie、Régis Guillot、Pierre Dorlet、Eric Rivière、Michel Desmadril、François Lambert、Clotilde Policar

  DOI：10.1021/ic1002379

  日期：2010.8.16

  In coordination chemistry, ligand shape can be used to tune properties, such as metal selectivity, coordination number, electronic structure, redox potential, and metal center stereochemistry including coordination helicates formation, and also to generate cavities for encapsulation. The results presented in this article indicate that two epimeric glycoligands (3 and 4) based on the conformationally

  在配位化学中，配体形状可用于调节特性，例如金属选择性，配位数，电子结构，氧化还原电势和金属中心立体化学（包括配位螺旋），还可以生成用于封装的腔体。本文中呈现的结果表明两个差向异构glycoligands（3和4基于所述构象约束）低聚木糖-和核糖-1,2- ö -isopropylidenefurano支架是在水通过π-π堆积预组织由于疏水相互作用，证明从准分子观察。固态获得的一种Cu（II）配合物的结构（5）是手性的，由于两个配体绕Cu-Cu轴盘绕而产生原始的螺旋手性。它显示了一种不寻常的双层结构，如电子顺磁共振所表明的那样，在两个三唑基-吡啶基环之间存在π-π相互作用，并且在两个Cu（II）离子之间具有一个小的空穴，能够容纳桥连的水分子。来自差向异构体配体（6）的Cu（II）配合物在Cu（II）的d-d区域具有类似的CD镜像性质。由C3构型6和5引起的糖配体在金属中心有一个手性的预先确定
• Intrinsically Fluorescent Glycoligands To Study Metal Selectivity
  作者：Ludivine Garcia、Stéphane Maisonneuve、Jennifer Oudinet-Sin Marcu、Régis Guillot、François Lambert、Juan Xie、Clotilde Policar

  DOI：10.1021/ic200897v

  日期：2011.11.21

  Glycoligands are a versatile family of ligands centered on a sugar platform and functionalized by Lewis bases. In this article, pentofuranoses were appended with the fluoroionophores 4-(pyridin-2'-yl)-1,2,3-triazol-1-yl and 4-(2',1',3'-benzothiadiazol-4'-yl)-1,2,3-triazol-1-yl using the "click-like" cycloaddition [2 + 3] of Huisgen catalyzed by copper(I). Their fluorescence properties were used to study metal cation complexation. A possible selective functionalization of furanoscaffolds allows the synthesis of "mixed" glycoligands with the successive insertion of these different fluoroionophores. The metal selectivity and the chelating behavior of these six resulting intrinsically fluorescent glycoligands were investigated. The change in the configuration at the carbon C3 of furanose did not influence either the metal selectivity or the binding constants. However, different selectivities and binding constants were found to depend on the nature of the fluoroionophore moieties. Overall, the triazolylbenzothiadiazolyl chelating group was shown to be less efficient than the triazolylpyridyl claw for complexation. Interestingly enough, the triazolylbenzothiadiazolyl claw, which fluoresces in the visible range, did not interfere in the binding and selectivity of the more efficient triazolylpyridyl claw. This study suggests that the triazolylbenzothiadiazolyl moiety could be used as an adequate fluorescent reporter to qualitatively monitor complexation of other moieties.