O¹,O²;O³,O⁴-diisopropylidene-O⁶-methyl-α-D-galactopyranose | 34698-17-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氧吡喃
• 英文名称: O¹,O²;O³,O⁴-diisopropylidene-O⁶-methyl-α-D-galactopyranose
• 英文别名: O¹,O²;O³,O⁴-Diisopropyliden-O⁶-methyl-α-D-galactopyranose；(1S,2R,6R,8R,9S)-8-(methoxymethyl)-4,4,11,11-tetramethyl-3,5,7,10,12-pentaoxatricyclo[7.3.0.02,6]dodecane
• CAS: 34698-17-4
• 化学式: C₁₃H₂₂O₆
• 分子量: 274.314
• InChiKey: XHYGPWYEBIJNLR-ZKKRXERASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  19
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  55.4
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  O¹,O²;O³,O⁴-diisopropylidene-O⁶-methyl-α-D-galactopyranose 在 lead(IV) acetate 、 硫酸 作用下， 以 水 、 溶剂黄146 为溶剂， 反应 9.67h， 生成 O⁴-methyl-D-threose
  参考文献：
  名称：

  未富集和[1-13C]富集的5-脱氧戊糖和5-O-甲基戊糖的合成和核磁共振光谱分析

  摘要：

  描述了用于制备D或L构型的未富集和[1-13C]富集的5-脱氧和5-O-甲基戊糖的化学方法。解释了这些化合物的1H-nmr光谱，并借助2-D 13C-1H化学位移相关光谱法指定了13C-nmr光谱。在2H2O溶液中的互变异构形式（呋喃糖，水合物和醛）已通过富含[1-13C]的衍生物进行了定量。为了评估5-C-脱氧和5-O-甲基化对化学位移和偶联常数（1H-1H，13C- 1H和13C-13C）和戊呋喃糖构象。

  DOI：

  10.1016/0008-6215(87)80180-5
• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 在 sodium hydroxide 、 丙酮 、 硫酸二甲酯 作用下， 生成 O¹,O²;O³,O⁴-diisopropylidene-O⁶-methyl-α-D-galactopyranose
  参考文献：
  名称：

  Reduction of the Products of Periodate Oxidation of Carbohydrates. IV. Hydrogenation with Palladium-Charcoal of the Dialdehydes from Methyl Glycosides^1,2

  摘要：

  DOI：

  10.1021/ja01560a051

文献信息

• Analysis of mixtures of some mono-O-methylaldoses with the common aldoses by g.l.c.-m.s. after isopropylidenation
  作者：Kai H. Aamlid、Svein Morgenlie

  DOI：10.1016/0008-6215(83)88350-5

  日期：1983.12

  Abstract The O-isopropylidene derivatives of seven naturally occurring mono-O-methylaldoses have been characterised by g.l.c.-m.s. G.l.c. conditions have been found under which almost complete separation of the O-methyl sugars and the common aldoses as their O-isopropylidene derivatives can be achieved. This analysis procedure has been applied to the hydrolysates of three polysaccharides that contain

  摘要已经通过glc-ms Glc条件表征了七个天然存在的单-O-甲基醛糖的O-异亚丙基衍生物，在该条件下，O-甲基糖和普通醛糖几乎可以完全分离，因为它们的O-异亚丙基衍生物可以被分离。实现。该分析程序已应用于含有O-甲基糖的三种多糖的水解产物。
• Reaktionen mit und in wasserfreiem Fluorwasserstoft 7.¹Von Isopropylidenzuckern zu acylierten Pyranosyl- oder Furanosylfluoriden in einem Schritt
  作者：Ralf Miethchen、Torsten Gabriel、Gundula Kolp

  DOI：10.1055/s-1991-26601

  日期：——

  Reactions with and in Anhydrous Hydrogen Fluoride 7.1 From Isopropylidene Sugars to Acylated Pyranosyl and Furanosyl Fluorides in One Step A convenient one-pot transformation of the 6-O-substituted 1,2:3,4-di-O-isopropylidene-α-D-galactopyranoses 1a-g and the 3-O-substituted 1,2:5,6-di-O-isopropylidene-α-D-glucofuranoses 5a-c is described to form the corresponding 6-O-substituted 2,3, 4-tri-O-acyl-α-D-galactopyranosyl fluorides 2a-f, 3e, 3g and 3-O-substituted 2,5,6-tri-O-acetyl-α/β-D-glucofuranosyl fluorides 6a-c, respectively. This short way of synthesis is possible by use of the new homogeneous reagent/catalyst/solvent combination composed of anhydrous hydrogen fluoride/nitromethane/carboxylic acid anhydride (2: 5:1-1.5). A ring contraction or extension is not found; in addition the functional groups are regiostable in 6-position of 2a-f, 3e, 3g and in 3-position of 6a-c, respectively.

  与无水氟化氢的反应 7.1 从异丙基糖到酰化吡喃糖和呋喃糖氟化物的一步法 一种便捷的单锅转化方法被描述，用于将6-O-取代的1,2:3,4-二-O-异丙基化α-D-半乳糖吡喃糖（1a-g）和3-O-取代的1,2:5,6-二-O-异丙基化α-D-葡萄糖呋喃糖（5a-c）转化为相应的6-O-取代的2,3,4-三-O-酰化α-D-半乳糖吡喃糖氟化物（2a-f, 3e, 3g）以及3-O-取代的2,5,6-三-O-乙酰化α/β-D-葡萄糖呋喃糖氟化物（6a-c）。这种简短的合成方法得益于新的均相试剂/催化剂/溶剂组合，包含无水氟化氢/硝基甲烷/羧酸酐（2:5:1-1.5）。未发现环收缩或扩展；此外，功能基团在2a-f, 3e, 3g的6位和6a-c的3位均表现出区域稳定性。
• A convenient selective synthesis of monosaccharide derivatives having only one free hydroxy group
  作者：Yu-Huei Chen、Tien-Yau Luh、Gene-Hsiang Lee、Shie-Ming Peng

  DOI：10.1039/c39940002369

  日期：——

  Reactions of acetonide derivatives of glucose, allose, galactose and fructose with MeMgI in benzene under reflux afford the corresponding monosaccharide derivatives having only one free hydroxy group in moderate to good yield.

  葡萄糖，阿糖，半乳糖和果糖的丙酮化物衍生物与MeMgI在苯中在回流下反应，得到相应的仅具有一个游离羟基的单糖衍生物，产率中等至良好。
• Chelation-Assisted Regioselective C−O Bond Cleavage Reactions of Acetals by Grignard Reagents. A General Procedure for the Regioselective Synthesis of Protected Polyols Having One Free Hydroxy Group
  作者：Wen-Lung Cheng、Yeng-Jeng Shaw、Sue-Min Yeh、Puthuparampil P. Kanakamma、Yu-Huey Chen、Chuo Chen、Jia-Cheng Shieu、Shaang-Jyh Yiin、Gene-Hsiang Lee、Yu Wang、Tien-Yau Luh

  DOI：10.1021/jo981579a

  日期：1999.1.1

  Acetals containing a neighboring heteroatom react with the Grignard reagent in aromatic hydrocarbon solvents regioselectively. The auxiliary moiety can be hydroxy, alkoxy, or amino but not sulfur. Chelation plays a key role in directing the regioselectivity of this ring opening reaction. The reactions of acetonide derivatives of monosaccharides under these conditions afford the corresponding products having only one free hydroxy group at the specific position. Fully protected mannosamine derivative is prepared in good yield. The stereochemistry of the carbon center where auxiliary group is attached can be either syn or anti to the acetal oxygen moiety where cleavage of the C-O bond occurs. However, difference in reactivity has been found in the reaction of tris-acetonide of sorbitol with MeMgI. Regioselective ring opening of the acetal group at the anomeric carbon generates a hemiacetal which underwent further nucleophilic addition to furnish the corresponding alcohol stereoselectively.
• Freudenberg; Hixon, Chemische Berichte, 1923, vol. 56, p. 2119,2125
  作者：Freudenberg、Hixon

  DOI：——

  日期：——