methyl 4-O-acetyl-3-azido-6-iodo-2,3,6-trideoxy-α-D-arabino-hexopyranoside | 421575-83-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 4-O-acetyl-3-azido-6-iodo-2,3,6-trideoxy-α-D-arabino-hexopyranoside
• 英文别名: [(2S,3S,4R,6S)-4-azido-2-(iodomethyl)-6-methoxyoxan-3-yl] acetate
• CAS: 421575-83-9
• 化学式: C₉H₁₄IN₃O₄
• 分子量: 355.132
• InChiKey: UYNANTBLWGUNOY-HXFLIBJXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  59.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4-O-acetyl-3-azido-6-iodo-2,3,6-trideoxy-α-D-arabino-hexopyranoside 在 吡啶 、 硫酸 、 盐酸羟胺 、 silver fluoride 作用下， 以 1,4-二氧六环 、 甲醇 为溶剂， 反应 49.25h， 生成 E-(2S,3R,5R)-2-乙酰氧基-3-叠氮-5-羟基环己酮肟
  参考文献：
  名称：

  From Tri‐O‐Acetyl‐D‐Glucal to (2R,3R,5R)‐2,3‐Diazido‐5‐Hydroxycyclohexanone Oxime

  摘要：

  Methyl 3-azido-2,3-dideoxy-alpha/beta-D-arabino- and -alpha/beta-D-ribo-hexopyranosides were transformed into 6-iodo analogues via p-tolylsulfonyl compounds. Elimination of hydrogen iodide from 6-iodo glycosides provided methyl 4-O-acetyl-3-azido-2,3,6-trideoxy-alpha- and -beta-D-threo-hex-5-eno-pyranosides or 3-azido-4-O-p-tolylsulfonyl-2,3,6-trideoxy-alpha-D-threo- and -beta-D-erythro-hex-5-eno-pyranosides. Ferrier's carbocyclization of 4-O-acetyl-3-azido-2,3,6-trideoxy-alpha- and -beta-D-threo-hex-5-eno-pyranosides gave (2S,3R,5R)-2-acetoxy-3-azido-5-hydroxycyclohcxanone, which was converted into oxime. The 2-OAc group in oxime was substituted by azide ion to yield (2R,3R,5R)-2,3-diazido-5-hydroxycyclohexanone oxime. The configuration and conformation of all products are widely discussed on the basis of the H-1 and C-13 NMR.

  DOI：

  10.1081/car-200040117
• 作为产物：
  描述：

  methyl 3-azido-2,3-dideoxy-6-O-tolylsulfonyl-α-D-arabino-hexopyranoside 在 吡啶 、 4-二甲氨基吡啶 、 sodium iodide 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 methyl 4-O-acetyl-3-azido-6-iodo-2,3,6-trideoxy-α-D-arabino-hexopyranoside
  参考文献：
  名称：

  甲基4-O-乙酰基-3-叠氮基-2,3,6-三苯氧基-6-碘-α-d-阿拉伯糖基己吡喃糖苷的合成，晶体结构和高分辨率NMR光谱

  摘要：

  室温下在甲苯中进行选择性甲苯磺酸化，然后将甲基3-叠氮基-2,3-二脱氧-α-D-阿拉伯糖基己吡喃糖苷（1）乙酰化，得到甲基4-O-乙酰基-3-叠氮基-2,3的混合物-双脱氧-6-二-Op-甲苯基磺酰基-α-D-阿拉伯糖基己吡喃糖苷（4）和甲基3-叠氮基-2,3-二脱氧-4,6-二-Op-甲苯基磺酰基-α-D-阿拉伯糖基己吡喃糖苷（3）。化合物4与碘化钠在乙酸酐中进行亲核取代，得到甲基4-O-乙酰基3-叠氮基2,3,6-三苯氧基-6-碘基-α-D-阿拉伯糖基六吡喃糖苷（7），其晶体结构报道了（1H）和（13）C NMR数据。该化合物采用4C（1）构象。

  DOI：

  10.1016/s0008-6215(01)00302-0

文献信息

• Determination of protolytic equilibria for methyl 3-azido-6-iodo-2,3,6-trideoxy-α-d-arabino-hexopyranoside by ab initio and spectrophotometric methods
  作者：Aleksandra Dąbrowska、Mariusz Makowski、Dagmara Jacewicz、Agnieszka Chylewska、Lech Chmurzyński

  DOI：10.1016/j.molstruc.2008.05.007

  日期：2008.12

  UV absorption spectra of methyl 3-azido-6-iodo-2,3,6-trideoxy-alpha-D-arabino-hexopyranoside were recorded over a wide pH range. On this basis, a relationship between absorbance and pH was plotted, from which deprotonation equilibrium constants of this compound were determined. Further, quantum-mechanical calculations were performed at the ab initio level both in the gas phase by using the Restricted Hartree Fock (RHF), Moller-Plesset (MP2) methods and under consideration of solvation effects within the Polarizable Continuum Model (PCM), which enabled location of preferred protonation and deprotonation centers of this compound. The results provided the basis for discussion of the influence of substituents in the sugar ring on protolytic equilibria occurring in aqueous solutions of 3-azido-2,3-dideoxy sugars. (C) 2008 Elsevier B.V. All rights reserved.