3,5-di-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose | 68095-72-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3,5-di-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose
• 英文别名: 3,5-Di-O-acetyl-1,2-O-isopropyliden-α-D-glucofuranose
• CAS: 68095-72-7
• 化学式: C₁₃H₂₀O₈
• 分子量: 304.297
• InChiKey: WAIWRTNOUILPCP-RMPHRYRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.28
• 重原子数：
  21.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  100.52
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  3,5-di-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose 、 乙酰溴-Alpha-D-葡萄糖酮酸甲基酯 在 silver carbonate 作用下， 以 二氯甲烷 为溶剂， 反应 36.0h， 以73.5%的产率得到methyl 2,3,4-tri-O-acetyl-β-D-glucopyranosyluronate-(1<*>6)-3,5-di-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Virtual 1H-1H spin-spin coupling in a linear five-spin system on the pyranose rings of some glucuronides

  摘要：

  In the H-1 NMR spectra of methyl 2,3,4-tri-O-acetyl-beta D-glucopyranosyluronate-(1 --> 3)- 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (6) and methyl 2,3,4-tri-O-acetyl-beta-D-glucopyranosyluronate-(l --> 6)-1,2:3,5-di-O-isopropylidene-alpha-D-glucofuranose (7), which were obtained by the reaction of 1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose (1) with methyl 2,3,4-tri-O-acetyl-alpha-D-glucopyranosyluronate bromide (5) in the presence of Hg(CN), in 1:1 benzene-nitromethane at 45 degrees C, protons on both beta-D-glucopyranosyluronate rings were observed as very complex signals that could not be interpreted by first-order analysis. Similar complex signals were also observed for the protons on the beta-D-glucopyranosyluronate rings that were sugar components of some triterpenoidal glycosides (13-15). These complex signals were determined to be due to virtual long-range spin-spin coupling in the linear five-spin system on the glucopyranosyluronate rings of the glucuronides by H-1, C-13, H-C COSY, 1D HOHAHA, and spin-simulation spectroscopies.

  DOI：

  10.1016/0008-6215(94)84075-x
• 作为产物：
  描述：

  1,2-O-isopropylidene-6-O-trityl-α-D-glucofuranose 在 吡啶 、 溶剂黄146 作用下， 反应 18.0h， 生成 3,5-di-O-acetyl-1,2-O-isopropylidene-α-D-glucofuranose
  参考文献：
  名称：

  Virtual 1H-1H spin-spin coupling in a linear five-spin system on the pyranose rings of some glucuronides

  摘要：

  In the H-1 NMR spectra of methyl 2,3,4-tri-O-acetyl-beta D-glucopyranosyluronate-(1 --> 3)- 1,2:5,6-di-O-isopropylidene-alpha-D-glucofuranose (6) and methyl 2,3,4-tri-O-acetyl-beta-D-glucopyranosyluronate-(l --> 6)-1,2:3,5-di-O-isopropylidene-alpha-D-glucofuranose (7), which were obtained by the reaction of 1,2;5,6-di-O-isopropylidene-alpha-D-glucofuranose (1) with methyl 2,3,4-tri-O-acetyl-alpha-D-glucopyranosyluronate bromide (5) in the presence of Hg(CN), in 1:1 benzene-nitromethane at 45 degrees C, protons on both beta-D-glucopyranosyluronate rings were observed as very complex signals that could not be interpreted by first-order analysis. Similar complex signals were also observed for the protons on the beta-D-glucopyranosyluronate rings that were sugar components of some triterpenoidal glycosides (13-15). These complex signals were determined to be due to virtual long-range spin-spin coupling in the linear five-spin system on the glucopyranosyluronate rings of the glucuronides by H-1, C-13, H-C COSY, 1D HOHAHA, and spin-simulation spectroscopies.

  DOI：

  10.1016/0008-6215(94)84075-x

文献信息

• Chromic acid oxidation in the synthesis of uronic acids. Use of the O-levulinoyl group to minimize acyl migration
  作者：Rabindra N. Rej、John N. Glushka、Warren Chew、Arthur S. Perlin

  DOI：10.1016/0008-6215(89)84092-3

  日期：1989.6

  include levulinoyl at O-5 of acylic and furanose derivatives, and both eq and ax O-4 of pyranose derivatives. It is also shown that, because of the acidity of the Jones reagent, use of the O -levulinoyl group, in combination with a primary p -anisyldiphenylmethyl substituent, permits sequential rapid hydrolysis of the latter and oxidation of the newly exposed alcohol group, which favors high overall yields

  摘要在部分酰化的糖衍生物的铬酸盐氧化反应中形成相应的糖醛酸时，酰基向伯醇基的迁移是干扰的常见原因。与更常用的酯取代基相比，在用琼斯试剂（铬硫酸）氧化的过程中，O-乙酰丙酰基的迁移率要低得多。这里描述的例子包括酰基和呋喃糖衍生物的O-5处的乙酰丙酰基，以及吡喃糖衍生物的eq Ox和ax O-4。还表明，由于琼斯试剂的酸性，将O-乙酰丙酰基与伯对-茴香基二苯基甲基取代基结合使用，可使后者顺序快速水解，并使新暴露的醇基氧化。有利于高总产。与它在这些氧化反应中的固定性相反，当乙酰丙酰基在醛糖基溴的O-2上时，它与O-乙酰基一样迅速地参与1,2-原酸酯的形成。d-吡喃葡萄糖苷甲基的任一异构体的2,3,4,6-四乙酸酯被铬酸在5：1乙酸-水中的氧化，以中等收率氧化为糖醛酸。
• Application of Ortho Esterification under Kinetically Controlled Conditions to the Selective Acylation in the D-Gluco-, D-Ribo- and D-Xylo-furanose Series
  作者：Mohamed Bouchra、Pierre Calinaud、Jacques Gelas

  DOI：10.1055/s-1995-3955

  日期：1995.5

  The ortho esterification of various glucofuranoses in the D-ribo-, D-xylo and D-gluco series under kinetic control was obtained through the action of 1,1-dimethoxyethene (a ketene acetal) on the monosaccharide using mild acid conditions. The selective hydrolysis of the methoxyethylidene derivatives thus obtained, gave access to α-hydroxy acetates which are useful synthetic intermediates.

  D-核糖、D-木糖和 D-葡萄糖系列中的各种呋喃葡萄糖在动力学控制下的原酯化是通过 1,1-二甲氧基乙烯（乙烯酮缩醛）在弱酸条件下与单糖的作用来实现的。由此获得的甲氧基亚乙基衍生物的选择性水解，得到α-羟基乙酸酯，这是有用的合成中间体。
• Klemer, Almuth; Bieber, Michael; Wilbers, Hubert, Liebigs Annalen der Chemie, 1983, # 8, p. 1416 - 1421
  作者：Klemer, Almuth、Bieber, Michael、Wilbers, Hubert

  DOI：——

  日期：——