methyl-(tetra-O-methyl-β-D-mannopyranoside) | 3445-71-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-(tetra-O-methyl-β-D-mannopyranoside)
• 英文别名: Methyl-(tetra-O-methyl-β-D-mannopyranosid)；(2R,3S,4S,5R,6R)-2,3,4,5-tetramethoxy-6-(methoxymethyl)tetrahydro-2H-pyran；(2R,3S,4S,5R,6R)-2,3,4,5-tetramethoxy-6-(methoxymethyl)oxane
• CAS: 3445-71-4
• 化学式: C₁₁H₂₂O₆
• 分子量: 250.292
• InChiKey: ZYGZAHUNAGVTEC-SAVGLBRCSA-N

物化性质

• 保留指数：
  1459

计算性质

• 辛醇/水分配系数(LogP)：
  -0.5
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  1.0
• 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

安全信息

• 海关编码：
  2932999099

反应信息

• 作为反应物：
  描述：

  methyl-(tetra-O-methyl-β-D-mannopyranoside) 在 dimethyl sulfide borane 、 丁基三氯化锡 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 生成 1,5-脱水甘露醇
  参考文献：
  名称：

  Reductive cleavage of permethylated polysaccharides with borane-methyl sulfide complex and butyltin trichloride

  摘要：

  Several per-O-methylated monosaccharides and polysaccharides were used as models in an attempt to identify more convenient reagents for accomplishing reductive cleavage of glycosidic linkages. Included in the model studies were methyl alpha- and beta-D-glucopyranoside, methyl alpha- and beta-D-mannopyranoside, and methyl alpha- and beta-D-ribofuranoside. These studies led to the identification of a new promoter, butyltin trichloride, for carrying out reductive cleavage when borane-methyl sulfide complex was used as the reducing agent. These reagents were found to accomplish the reductive cleavage of per-O-methylated amylose, cellulose, and pullulan to give only the expected derivatives of 1,5-anhydro-D-glucitol. These reagents also accomplished reductive cleavage of per-O-methylated inulin to give only the expected derivatives of 2,5-anhydro-D-mannitol and 2,5-anhydro-D-glucitol. Reductive cleavage using these reagents is easy to perform, and subsequent acetylation of the products is readily accomplished in situ. (C) 1997 Elsevier Science Ltd.

  DOI：

  10.1016/s0008-6215(96)00312-6
• 作为产物：
  描述：

  2,3,4,6-tetra-O-methyl-D-mannono-1,5-lactone 在 吡啶 、 ruthenium(IV) oxide 、 sodium periodate 、 molecular sieve 、 C₆H₄NO₂S⁺Cl^- 、 三氟化硼乙醚 、 silver trifluoromethanesulfonate 、 叔丁基硫醇 、 三乙胺 作用下， 以 四氢呋喃 、 四氯化碳 、 二氯甲烷 、 乙腈 为溶剂， 反应 57.33h， 生成 methyl-(tetra-O-methyl-β-D-mannopyranoside)
  参考文献：
  名称：

  1-烷氧基-1-糖基自由基的化学：通过甘露庚糖酸糖苷衍生物的自由基脱羧和脱羰作用形成β-甘露吡喃糖苷。

  摘要：

  描述了一种制备高度浓缩的β-甘露聚糖的方法。通过标准方法由四烯丙基甘露糖内酯制备糖基供体28，并将其与许多伯糖醇偶联，从而以极高的产率获得了轴向二糖。在将烯丙基交换为乙酰基酯后，呋喃被催化RuO（2）和NaIO（4）氧化裂解，所得酸经过Barton脱羧。28与仲醇2,3-异亚丙基-α-L-鼠李糖吡喃糖苷的偶合导致异头异构体化学结构的明显倒置和赤道二糖的分离。

  DOI：

  10.1021/jo960799q

文献信息

• 1 : 1 Adduct Ion Formation of Permethylated Monosaccharides with Organic Cations in FAB Mass Spectrometry
  作者：Masami Sawada、Li Ouyang、Yoshio Takai、Hitoshi Yamada、Motohiro Shizuma、Takeshi Kinoshita、Tomoko Mochizuki、Terukiyo Hanafusa

  DOI：10.1246/bcsj.64.1243

  日期：1991.4

  the OCH3 configurational effects of M on (M+A)+ adduct ion formation. The findings can be interpreted in terms of multisite electrostatic interaction of oxygens with the cation. Coupled with the results of gas-phase behavior by FABMS/MS(CAD), solution behavior by 1H NMR, and model calculations by MNDO, the characteristic structure of the 1 : 1 adduct ion is deduced as host-guest type association between

  已在定量 FAB 质谱法中检查了一系列全甲基化单糖 (M; Ia–Ih) 和有机或金属阳离子 (A+) 之间 1:1 的加合离子形成。在相同 FABMS 条件下的仔细比较中，相对 (M+A)+ 峰强度以单糖的以下顺序增加，并进一步以几乎相同的程度增加，尽管使用了三种不同的阳离子，例如辛基铵，（甲氧基羰基） ) 甲基铵和钾离子：β-Glc<α-Glc<α-Gal<β-Gal≤α-Man<β-Man<α-Tal<β-Tal。顺序和阳离子独立性清楚地表明 OCH3 构型M 对 (M+A)+ 加合离子形成的影响。这些发现可以解释为氧与阳离子的多位点静电相互作用。
• Mechanism of anomerization of permethylated methyl d-glycopyranosides by trimethylsilyl trifluoromethanesulfonate
  作者：Chang Kiu Lee、Eun Ju Kim、In-Sook Han Lee

  DOI：10.1016/s0008-6215(98)00132-3

  日期：1998.7

  Abstract Anomerization of permethylated methyl d -glycopyranosides catalyzed by trimethylsilyl trifluoromethanesulfonate was examined by NMR spectroscopy and gas–liquid chromatography. The initial-rate analysis showed that the rates of anomerization of β to α were faster than those of the opposite at various concentrations of the catalyst. The overall rates of disappearance of the substrates were faster

  摘要用三氟甲磺酸三甲基甲硅烷基酯（NMR）和气相色谱法研究了全甲基化的甲基d-吡喃葡萄糖苷的三元甲硅烷基化反应。初始速率分析表明，在不同的催化剂浓度下，β到α的异化速率要快于相反的速率。底物的总消失速率比相反的端基异构体的出现速率快，这是因为形成了yl型化合物。后者的结构是基于1 H和13 C NMR光谱提出的，尽管它是不可分离的。环状和无环的氧鎓离子似乎都是异构化的中间体。前者似乎是形成吡啶型化合物以及α-糖苷键的异构化的关键中间体。
• Anomerization and transglycosylation reactions of permethylated methyl d-glycopyranosides
  作者：Chang Kiu Lee、Eun Ju Kim、In-Sook Han Lee

  DOI：10.1016/0008-6215(93)84183-7

  日期：1993.2

  Abstract The anomerization reactions of permethylated methyl d -glycopyranosides in the presence of various Lewis acid catalysts, such as Me3SiOTf, Me3SiOMs, BF3·OEt2, or TiCl4 were examined in dichloromethane solution. β Anomers of the glycosides anomerized to the α anomer very rapidly, but the anomerizations in the opposite direction were slower. Transglycosylation reactions of the glycosides in the

  摘要研究了在二氯甲烷溶液中，在各种路易斯酸催化剂（如Me3SiOTf，Me3SiOMs，BF3·OEt2或TiCl4）存在下，全甲基化甲基d-吡喃吡喃糖苷的异构化反应。糖苷的β端基异构体非常快地异构化为α端基异构体，但反方向的端基异构化则较慢。在相似的催化剂和乙醇的存在下，糖苷的转糖基化反应优选产生具有大多数底物的α端基异构体。在α-甘露糖苷的情况下未观察到异构化，这可能是因为在平衡时α-异构体被强烈青睐。然而，转糖基化发生了。
• Exploring the Far Side of Glycosyl Sulfoxide Activation Process
  作者：Wei Chen、Pinru Wu、Jing Zeng、Jing Fang、Zhiwen Liao、Lei Cai、Hao Wang、Lingkui Meng、Qian Wan

  DOI：10.1002/cjoc.202200706

  日期：2023.2.15

  an extensive series of studies, the precise mechanism of this powerful glycosylation is still not fully understood. To address these 30-year puzzles, the far side of Kahne glycosylation is explored in this study. After a series of control and tracking experiments, a number of important intermediates including glycosyl oxo-sulfonium ion and sulfenic anhydride (Crich's intermediate) are suggested to be

  Kahne 糖基化的发现使碳水化合物化学向前迈进了一大步。尽管进行了一系列广泛的研究，但这种强大的糖基化作用的确切机制仍未完全了解。为了解决这些 30 年的难题，本研究探索了 Kahne 糖基化的另一面。经过一系列的控制和跟踪实验，一些重要的中间体包括糖基氧代硫离子和亚磺酸酐（Crich 中间体）被认为是复杂反应途径的原因。它还表明，除了传统的离子糖基化途径外，一种新的自由基途径很可能有助于产生各种副产物和副产物。这项研究提供了对 Kahne 糖基化的进一步了解，
• Bott et al., Journal of the Chemical Society, 1930, p. 2653,2655
  作者：Bott et al.

  DOI：——

  日期：——