methyl 4,6-O-methylidene-α-D-glucopyranoside | 50256-48-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: methyl 4,6-O-methylidene-α-D-glucopyranoside
• 英文别名: (4aR,6S,7R,8R,8aS)-6-methoxy-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxine-7,8-diol
• CAS: 50256-48-9
• 化学式: C₈H₁₄O₆
• 分子量: 206.196
• InChiKey: SCPZHNFZLGNUMI-PVFLNQBWSA-N

物化性质

• 沸点：
  377.4±42.0 °C(Predicted)
• 密度：
  1.40±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.7
• 重原子数：
  14
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  77.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  methyl 4,6-O-methylidene-α-D-glucopyranoside 在 sodium periodate 作用下， 以 水 为溶剂， 反应 24.0h， 以37%的产率得到
  参考文献：
  名称：

  Structure and Reactions of Glycopyranoside Derived Dialdehydes

  摘要：

  Several 4- protected D-glucopyranosides were synthesized and cleaved by sodium metaperiodate. Depending on the protection pattern the resulting dialdehydes showed different types of structures. Predominantly dioxane structures of the hemiacetal or hemialdal type were obtained with preferred trans orientation of the exo oxygen groups at C-1 and C-2. The dialdehyde derived from methyl 4-O-methyl-alpha-D-glucopyranoside was treated with various C-nucleophiles. A higher reactivity of the aldehyde function at the former C-3 in comparison to C-2 and a special stability of dioxane type structures for glycol cleavage dialdehydes derived was observed.

  DOI：

  10.1002/prac.19983400305
• 作为产物：
  描述：

  methyl 2,3-di-O-benzyl-4,6-O-methylidene-α-D-glucopyranoside 在 palladium on activated charcoal 氢气 作用下， 以 甲醇 为溶剂， 生成 methyl 4,6-O-methylidene-α-D-glucopyranoside
  参考文献：
  名称：

  Structure and Reactions of Glycopyranoside Derived Dialdehydes

  摘要：

  Several 4- protected D-glucopyranosides were synthesized and cleaved by sodium metaperiodate. Depending on the protection pattern the resulting dialdehydes showed different types of structures. Predominantly dioxane structures of the hemiacetal or hemialdal type were obtained with preferred trans orientation of the exo oxygen groups at C-1 and C-2. The dialdehyde derived from methyl 4-O-methyl-alpha-D-glucopyranoside was treated with various C-nucleophiles. A higher reactivity of the aldehyde function at the former C-3 in comparison to C-2 and a special stability of dioxane type structures for glycol cleavage dialdehydes derived was observed.

  DOI：

  10.1002/prac.19983400305

文献信息

• Site-Selective Acylation of Pyranosides with Oligopeptide Catalysts
  作者：Alexander Seitz、Raffael C. Wende、Emily Roesner、Dominik Niedek、Christopher Topp、Avene C. Colgan、Eoghan M. McGarrigle、Peter R. Schreiner

  DOI：10.1021/acs.joc.0c02772

  日期：2021.3.5

  monosaccharides. We identified catalysts that invert site-selectivity compared to N-methylimidazole, which was used to determine the intrinsic reactivity, for 4,6-O-protected glucopyranosides (trans-diols) as well as 4,6-O-protected mannopyranosides (cis-diols). The reaction yields up to 81% of the inherently unfavored 2-O-acetylated products with selectivities up to 15:1 using mild reaction conditions. We also

  在此，我们报道了部分保护的单糖的寡肽催化的位点选择性酰化。我们确定了催化剂，其反转的网站选择性相比ñ甲基咪唑，这是用来确定内在反应，为4,6- Ø重保护的吡喃葡萄糖苷（反式-diols）以及4,6- Ø -protected mannopyranosides（顺-二醇）。在温和的反应条件下，该反应产生高达81％的固有不利的2- O-乙酰化产物，选择性高达15：1。我们还确定了保护基对反应的影响，并证明我们的方案适用于具有多个连续保护步骤的一锅法反应。
• Site-Selective Acylations with Tailor-Made Catalysts
  作者：Florian Huber、Stefan F. Kirsch

  DOI：10.1002/chem.201600790

  日期：2016.4.18

  The acylation of alcohols catalyzed by N,N‐dimethylamino pyridine (DMAP) is, despite its widespread use, sometimes confronted with substrate‐specific problems: For example, target compounds with multiple hydroxy groups may show insufficient selectivity for one hydroxyl, and the resulting product mixtures are hardly separable. Here we describe a concept that aims at tailor‐made catalysts for the site‐specific

  N，N催化醇的酰化反应二甲氨基吡啶（DMAP）尽管已被广泛使用，但有时仍会遇到特定于底物的问题：例如，具有多个羟基的目标化合物可能对一个羟基的选择性不足，并且所得产物混合物几乎不可分离。在这里，我们描述了一种旨在针对特定位点的酰化量身定制催化剂的概念。为此，我们介绍了一个催化剂库，其中的每个条目都是通过将可变且易于调节的肽支架与基于DMAP的催化活性单元相连接而构建的。对于选定的例子，我们演示了库筛选如何导致优化催化剂的鉴定，并且与仅DMAP相比，目标底物可以显着提高的位点选择性转化。此外，
• Catalytic Site-Selective Acylation of Carbohydrates Directed by Cation–<i>n</i> Interaction
  作者：Guozhi Xiao、Gabriel A. Cintron-Rosado、Daniel A. Glazier、Bao-min Xi、Can Liu、Peng Liu、Weiping Tang

  DOI：10.1021/jacs.7b01412

  日期：2017.3.29

  Site-selective functionalization of hydroxyl groups in carbohydrates is one of the long-standing challenges in chemistry. Using a pair of chiral catalysts, we now can differentiate the most prevalent trans-1,2-diols in pyranoses systematically and predictably. Density functional theory (DFT) calculations indicate that the key determining factor for the selectivity is the presence or absence of a cation-n interaction between the cation in the acylated catalyst and an appropriate lone pair in the substrate. DFT calculations also provided a predictive model for site-selectivity and this model is validated by various substrates.
• Réaction de Transacétalisation par le Diméthoxyrnéthane synthése de O-méthylèneacétal de dérivés du D(+)Glucose
  作者：Robert Nouguier、Jean-Louis Gras

  DOI：10.1016/s0040-4020(01)81020-6

  日期：1989.1
• Synthesis of methylene acetals in the d-glucose, d-galactose, d-mannose, and d-fructose series by an improved transacetalation reaction from dimethoxymethane
  作者：Robert Nouguier、Valérie Mignon、Jean-Louis Gras

  DOI：10.1016/0008-6215(95)00218-i

  日期：1995.11