methyl 3-azido-4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside | 1038395-32-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 3-azido-4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside
• 英文别名: 3-azido-4,6-O-benzylidene-3-deoxy-D-glucopyranoside；(2R,4aR,6S,7R,8R,8aS)-8-azido-6-methoxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol
• CAS: 1038395-32-2
• 化学式: C₁₄H₁₇N₃O₅
• 分子量: 307.306
• InChiKey: RNDFEGLTMSTFOF-UQPQVDFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  22
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  71.5
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  methyl 3-azido-4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 二乙胺基三氟化硫 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 78.0h， 生成 2,5-anhydro-3-azido-6-O-tert-butyl-diphenylsilyl-3,4-dideoxy-1,4-difluoro-1-O-methyl-D-talitol
  参考文献：
  名称：

  Fluorination of 2-hydroxy-hexopyranosides by DAST: towards formyl C-glycofuranosides from equatorial-2-OH methyl hexopyranosides

  摘要：

  Reaction of diversely configured and substituted, unbranched methyl D-hexopyranosides with the DAST in dichloromethane or acetonitrile led to normal substitution products and/or rearranged fluoro compounds (ring-contracted 2,5-anhydro-1-fluoro-1-I-methylhexitol derivatives, 2-methoxy-D-hexopyranosyl fluorides, and, for some 3-azido substrates, rearranged 2-azido-3-fluoro-D-hexopyranosides). When the reaction was performed in acetonitrile, the solvent participation as a nucleophile (Ritter reaction) was observed in one case. For a 2,4-unprotected 3-azido substrate, 2,3-dehydration and fluorination at C(4), the latter with epimerization, took place. F-19/H-1 and F-19/C-13 coupling constant values were systematically applied to discriminate between isomeric structures for fluorinated products, and for some, previously described, coming from five 3-branched-chain D- or L-hexopyranosides, thus discarding the previously reported structural assignment. From the synthetic point of view, the most outstanding result was the preparation of 2,5-anhydro-1-fluoro-1-O-methylhexitols, showing a latent formyl group functionality, a transformation, which was achieved in one case. A rationalization for the formation of the different types of product is also proposed. (C) 2003 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2003.11.034
• 作为产物：
  描述：

  Methyl 3-azido-3-deoxy-α-D-glucopyranoside 、 苯甲醛二甲缩醛 在 D(+)-10-樟脑磺酸 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以76%的产率得到methyl 3-azido-4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  Chemoenzymatic synthesis of GDP-azidodeoxymannoses: non-radioactive probes for mannosyltransferase activity

  摘要：

  利用肠炎沙门氏菌的 GDP-甘露糖焦磷酸酶（GDP-ManPP），可以成功地从相应的叠氮甘露糖-1-磷酸酯和 GTP 中制备出 GDP-2-、3-、4-或 6-叠氮甘露糖，并可作为甘露糖基转移酶活性的有用探针。

  DOI：

  10.1039/b807016d

文献信息

• Toward Fluorinated Aminoglycosides: Structural Studies of Phenylhydrazine Condensation with Carbohydrate Derivatives
  作者：Antonio Franconetti、Francisca Cabrera-Escribano、Pastora Borrachero、Manuel Gómez-Guillén

  DOI：10.1055/s-0032-1317783

  日期：——

  The reaction of phenylhydrazine with a sugar dialdehyde in water, as a key step for the synthesis of the 3-amino-3-deoxy- d -glucose moiety contained in kanamycin, has been revisited. Structural studies (IR and NMR as well as a simple theoretical model based on energy-minimization calculations and MD calculations) reported herein support the observed stereo- and regioselectivity. Efforts to improve

  苯肼与糖二醛在水中的反应是合成卡那霉素中含有的 3-氨基-3-脱氧-d-葡萄糖部分的关键步骤。本文报道的结构研究（IR 和 NMR 以及基于能量最小化计算和 MD 计算的简单理论模型）支持观察到的立体选择性和区域选择性。现在还介绍了提高该过程的再现性和可行性的努力，作为氟化卡那霉素的便捷方法的一部分。
• Aldotetroses and C(3)-Modified Aldohexoses as Substrates for N-Acetylneuraminic Acid Aldolase: A Model for the Explanation of the Normal and the Inversed Stereoselectivity
  作者：Wolfgang Fitz、Jan-Robert Schwark、Chi-Huey Wong

  DOI：10.1021/jo00117a016

  日期：1995.6

  The four stereoisomeric aldotetroses were accepted with different reactivities by N-acetylneuraminic acid aldolase. C(3)-modified D-mannose and D-glucose derivatives, respectively, failed to undergo enzymatic aldol addition. Based on the observed reactivities of the tested compounds (about 58), a mechanistic scheme is proposed which relates substrate structure, reactivity and stereochemical outcome observed in Neu5Ac aldolase-catalyzed reactions. The condensation products obtained in the L-erythrose and D-threose reactions are side-chain modified sialic acid and D-KDO derivatives, respectively, of biological interest.