methyl 3,4,6-tri-O-methyl-β-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,4,6-tri-O-methyl-β-D-glucopyranoside
• 英文别名: methyl 3,4,6-tri-O-methyl-glucopyranoside；(2R,3R,4R,5R,6R)-2,4,5-trimethoxy-6-(methoxymethyl)oxan-3-ol
• 化学式: C₁₀H₂₀O₆
• 分子量: 236.265
• InChiKey: MJCQVUQCEVACLB-VVULQXIFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -1
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  66.4
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 3,4,6-tri-O-methyl-β-D-glucopyranoside 在 盐酸 作用下， 生成 (2R,3R,4R,5R)-2,5-二羟基-3,4,6-三甲氧基己醛
  参考文献：
  名称：

  A New Synthesis of Methyl 3,4,6-Trimethyl-β-d-glucoside and the Preparation of Crystalline 3,4,6-Trimethyl-d-glucose

  摘要：

  DOI：

  10.1021/ja01223a018
• 作为产物：
  描述：

  methyl-(O²-benzyl-O³-methyl-β-D-glucopyranoside) 在 sodium hydroxide 、 palladium on activated charcoal 、 溶剂黄146 作用下， 生成 methyl 3,4,6-tri-O-methyl-β-D-glucopyranoside
  参考文献：
  名称：

  A New Synthesis of Methyl 3,4,6-Trimethyl-β-d-glucoside and the Preparation of Crystalline 3,4,6-Trimethyl-d-glucose

  摘要：

  DOI：

  10.1021/ja01223a018

文献信息

• Study on the constituents of Desmodium styracifolium.
  作者：Tomoko KUBO、Syuichi HAMADA、Toshihiro NOHARA、Zhi-rou WANG、Hideo HIRAYAMA、Keiichi IKEGAMI、Ken YASUKAWA、Michio TAKIDO

  DOI：10.1248/cpb.37.2229

  日期：——

  Two triterpenoid saponins (1 and 2) were isolated from Desmodii Herba [the dried whole plants of Desmodium styracifolium (Osbeck) Merr. (Leguminosae)] and their chemical structures were characterized as soyasaponin I and a new saponin, 3-O-[alpha-L-rhamnopyranosyl-(1----2)-beta-D-galactopyranosyl- (1----2)-beta-D-glucuronopyranosyl]soyasapogenol E, respectively, by chemical and spectroscopic means

  从Desmodii Herba [满地香（Desmodium styracifolium（Osbeck）Merr）干燥的整株植物中分离出了两个三萜皂苷（1和2）。（豆科）]及其化学结构被表征为大豆皂苷I和新的皂苷3-O- [α-L-鼠李糖基-（1 ---- 2）-β-D-吡喃半乳糖基-（1 ---- 2）通过化学和光谱方法分别测定β-D-D-葡萄糖醛酸吡喃糖基]大豆皂酚E。
• Tandem Epoxidation‐Alcoholysis or Epoxidation‐Hydrolysis of Glycals Catalyzed by Titanium(IV) Isopropoxide or Venturello’s Phosphotungstate Complex
  作者：Pieter Levecque、David W. Gammon、Henok Hadgu Kinfe、Pierre Jacobs、Dirk De Vos、Bert Sels

  DOI：10.1002/adsc.200800079

  日期：2008.7.7

  Venturello’s phosphotungstate complex and titanium(IV) isopropoxide [Ti(O-i-Pr)4] were successfully used as catalysts for the epoxidation-alcoholysis of glycals using hydrogen peroxide [H2O2]. Reaction substrates included a range of variously protected glycals and different alcohols were used as solvents. Ti(O-i-Pr)4 was only effective in methanol as solvent, but gave methyl glycosides in high yields

  Venturello的磷钨酸盐络合物和异丙醇钛（IV）[Ti（O- i- Pr）4 ]已成功用作使用过氧化氢[H 2 O 2 ]的环氧乙烷缩合醇解的催化剂。反应底物包括各种受保护的糖基，不同的醇用作溶剂。钛（O- i- Pr）4仅在甲醇作为溶剂中有效，但以高收率和高选择性得到甲基糖苷。事实证明，Ventrollo复合物是一种用途广泛且高效的催化剂。除了在醇类溶剂中进行环氧化-醇解以外，它还显示了在双相条件下的活性，以允许长链醇的糖基化，并且在苄基化的葡糖的立体选择性二羟基化中非常有效。
• Hydroxy Group Acidities of Partially Protected Glycopyranosides
  作者：Martin Matwiejuk、Joachim Thiem

  DOI：10.1002/ejoc.201101708

  日期：2012.4

  A comprehensive acidity study of carbohydrate hydroxy groups has been carried out. Relative acidities (Ke) were determined spectrophotometrically for partially methylated methyl α-D-glycopyranosides. Apparently, the acidity is strongly affected by intramolecular hydrogen bonding as well as stereochemistry and solvation. By comparison with pKe and pKa values of aliphatic alcohols and polyols the first

  已经进行了碳水化合物羟基的综合酸度研究。对于部分甲基化的甲基 α-D-吡喃糖苷，通过分光光度法测定相对酸度 (Ke)。显然，酸度受分子内氢键以及立体化学和溶剂化的强烈影响。通过与脂肪醇和多元醇的 pKe 和 pKa 值进行比较，获得了部分保护的吡喃糖苷的 pKa 值的首次估计值。这些发现有助于理解碳水化合物羟基的相对反应性。
• Triterpene and steroidal glycosides of the genus Melilotus and their genins. VI. Melilotoside A2 and adzukisaponin V from the roots of M. tauricus
  作者：G. V. Khodakov

  DOI：10.1007/s10600-013-0455-x

  日期：2013.1

  Two triterpene glycosides of the oleanane series, melilotoside A2 and previously known adzukisaponin V, were isolated from the roots of Melilotus tauricus (L.) Pall. (Fabaceae). The structures of the glycosides were proved based on chemical transformations. Melilotoside A2 had the structure soyasapogenol B 3-O-β-D-glucouronopyranoside; adzukisaponin V, soyasapogenol B 3-O-[α-L-rhamnopyranosyl-(1-2)-β-Dglucopyranosyl-(1-2)-β-D-glucuronopyranoside].

  从 Melilotus tauricus (L.) Pall.（豆科植物）的根中分离出了两种齐墩果烷系列的三萜苷，即 Melilotoside A2 和以前已知的 adzukisaponin V。(豆科）根中分离出来。这些苷的结构是通过化学转化得到证实的。Melilotoside A2 的结构为 soyasapogenol B 3-O-β-D-glucouronopyranoside; adzukisaponin V, soyasapogenol B 3-O-[α-L-rhamnopyranosyl-(1-2)-β-Dglucopyranosyl-(1-2)-β-D-glucuronopyranoside].
• The chemistry of glucal halohydrins: The effect of the halide on epoxide formation
  作者：Cecilia H. Marzabadi、Christopher D. Spilling、Lisa M. Tyler

  DOI：10.1016/s0040-4020(01)81332-6

  日期：1994.1

  Chlorohydrins, bromohydrins, and iodohydrins, formed by hydroxyhalogenation of tri-O-methyl glucal, undergo base induced cyclization to give glucal epoxides. The mechanism of the cyclization reaction was probed using 1H NMR and deuterium incorporation studies. Cyclization and in situ trapping with Cs2CO3 in MeOD gave deuterated methyl 3,4,6-tri-O-methyl-α-D-mannoside and methyl 3,4,6-tri-O-methyl-β-D-glucoside

  由三-O-甲基葡糖基的羟基卤化作用形成的氯醇，溴代醇和碘代醇经碱诱导的环化反应生成葡糖基环氧化物。使用1 H NMR和氘掺入研究探索了环化反应的机理。Cs 2 CO 3的环化和原位捕集在MeOD中得到氘化的甲基3,4,6-三-O-甲基-α-D-甘露糖苷和甲基3,4,6-三-O-甲基-β-D-葡萄糖苷和不饱和醛。这些研究导致环氧化物形成的优化的立体选择性。葡萄糖溴醇与NaH或LiHMDS在THF中于5°C反应，生成β-环氧化物，甘露糖碘醇与KH和18-crown-6在甲苯中，于-70°C反应，生成α-环氧化物。通过与苯硫醇钠反应打开环氧化物，得到苯基3,4,6-三-O-甲基-1-硫代-α-D-甘露吡喃糖苷（单一异构体）和苯基3,4,6-三-O-苯基甲基-1-硫代-β-D-吡喃葡萄糖苷（18：1）。