methyl 2,3,4-tri-O-acetyl-6-deoxy-α-D-glucopyranoside | 19940-17-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-acetyl-6-deoxy-α-D-glucopyranoside
• 英文别名: α-1-methoxy-2,3,4-O-acetyl-D-quinovose；methyl-(tri-O-acetyl-6-deoxy-α-D-glucopyranoside)；Methyl-(tri-O-acetyl-6-desoxy-α-D-glucopyranosid)；(2S,3R,4S,5R,6R)-2-methoxy-6-methyltetrahydro-2H-pyran-3,4,5-triyl triacetate；[(2R,3R,4S,5R,6S)-4,5-diacetyloxy-6-methoxy-2-methyloxan-3-yl] acetate
• CAS: 19940-17-1
• 化学式: C₁₃H₂₀O₈
• 分子量: 304.297
• InChiKey: RTVWBDNQHISFHI-QPSDPIORSA-N

物化性质

• 熔点：
  75 °C
• 沸点：
  341.4±42.0 °C(Predicted)
• 密度：
  1.21±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  97.4
• 氢给体数：
  0
• 氢受体数：
  8

安全信息

• 储存条件：
  2-8°C

反应信息

• 作为反应物：
  描述：

  methyl 2,3,4-tri-O-acetyl-6-deoxy-α-D-glucopyranoside 在 氢溴酸 、 溶剂黄146 、 silver carbonate 作用下， 生成 methyl 2,3,4-tri-O-acetyl-6-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  The Unimolar Tosylation¹ of alpha- and beta-Methyl-d-glucosides

  摘要：

  DOI：

  10.1021/ja01269a045
• 作为产物：
  描述：

  alpha-甲基葡萄糖甙 在 吡啶 、 咪唑 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 碘 、 三正丁基氢锡 、 三苯基膦 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 6.0h， 生成 methyl 2,3,4-tri-O-acetyl-6-deoxy-α-D-glucopyranoside
  参考文献：
  名称：

  三氯化硼 (BCl3) 对全乙酰化脱氧-C-吡喃糖苷进行区域选择性脱乙酰化

  摘要：

  开发了由 BCl 3介导的全乙酰化 6-脱氧-C-吡喃葡萄糖苷的糖 3-OH 区域选择性脱乙酰化的通用方法。该方法可以扩展到其他糖衍生的 6-脱氧-C-吡喃葡萄糖苷，例如衍生自甘露糖、半乳糖和鼠李糖的那些，在不同的糖羟基上发生脱乙酰化，并进一步扩展到 4-脱氧-C-吡喃葡萄糖苷糖3-OH处发生脱乙酰化。该方法将能够获得具有合成挑战性的碳水化合物衍生物。提出了区域选择性的可能机制。

  DOI：

  10.1021/acs.joc.4c00026

文献信息

• Utilization of Sugars in Organic Synthesis. XXIII. Part XXII: Lithium Aluminum Hydride Reduction of Glycopyranoside-Monosulfonates: Formation of Branched Furanosides.
  作者：Yoshisuke TSUDA、Makoto NISHIMURA、Yoko ITO

  DOI：10.1248/cpb.39.1983

  日期：——

  Lithium aluminum hydride reduction of glycopyranoside-monotosylates caused three reactions : (1) stereospecific 1, 2-shift, producing branched furanosides (path A), (2) reductive O-S bond cleavage, producing the original glycosides (path B), and (3) reductive removal of the tosyloxy group, producing deoxyglycosides (path C). The path A reaction was particularly evident for the monotosylates at 2-O, 3-O, and 4-O : for example, methyl 2-O-tosyl-α-D-xylopyranoside gave methyl 2-deoxy-2-C-(hydroxymethyl)-α-D-erythrofuranoside in 60% yield. This reaction opens a new and efficient route to branched glycofuranosides of natural and unnatural type. Stereo-electronic requirements of this reaction in relation to the balance of the other two reactions are discussed.

  乙醇醛糖苷-单甲磺酸酯的锂铝氢还原引发了三种反应：(1) 立体特异性的1,2-移位，生成分支呋喃糖苷(路径A)，(2) 还原性O-S键断裂，生成原始糖苷(路径B)，以及(3) 甲磺酰氧基的还原性移除，生成去氧糖苷(路径C)。在2-O、3-O和4-O位置的单甲磺酸酯中，路径A反应尤为显著；例如，甲基2-O-甲磺酰-α-D-木糖吡喃糖苷以60%的产率转化为甲基2-脱氧-2-C-(羟甲基)-α-D-赤藓呋喃糖苷。该反应为天然与非天然型分支糖呋喃糖苷的合成开辟了一条新颖高效的途径。本反应的立体电子学需求与其余两种反应的平衡关系在此讨论。
• Conversion of Alkyl Halides into Alcohols Using a Near Stoichiometric Amount of Molecular Oxygen: An Efficient Route to ¹⁸O- and ¹⁷O-Labeled Alcohols
  作者：Masaya Sawamura、Yasuhide Kawaguchi、Eiichi Nakamura

  DOI：10.1055/s-1997-5779

  日期：1997.7

  In the presence of near stoichiometric amount of molecular oxygen, various alkyl halides were converted to the corresponding alcohols in high yields through aerobic radical reaction promoted by a Bu2(t-Bu)SnCl/NaBH3CN catalytic system. Isotope-labeled alcohols were prepared with 18O2 and 17O2 without loss of the isotopic purities of the starting oxygen gases.

  在接近化学计量的分子氧存在下，多种卤代烷通过Bu2(t-Bu)SnCl/NaBH3CN催化体系促进的需氧自由基反应高产率地转化为相应的醇。采用18O2和17O2制备同位素标记的醇，且起始氧气同位素纯度未受损。
• Partially Benzylated Derivatives of 6-Deoxy-D-glucose
  作者：Shinkiti Koto、Naohiko Morishima、Yoko Mori、Hitoshi Tanaka、Seiichi Hayashi、Yumi Iwai、Shonosuke Zen

  DOI：10.1246/bcsj.60.2301

  日期：1987.6

  Several partially benzylated derivatives of 6-deoxy-d-glucose (d-quinovose) were synthesized from appropriate di-O-benzyl-d-glucosides whose primary hydroxyl group is unprotected, via unimolar tosylation and subsequent reduction with LiAlH4.

  通过单摩尔数量的甲苯磺酰化反应和随后的LiAlH4还原反应，从适当的二-O-苄基-d-葡糖苷（其伯羟基未保护）合成了6-脱氧-d-葡萄糖（d-黄花草糖）的几种部分苄基化衍生物。
• Radical Rearrangements of 2-O-(Diphenoxyphosphoryl)glycosyl Bromides
  作者：Andreass Koch、Bernd Giese

  DOI：10.1002/hlca.19930760426

  日期：1993.6.30

  2-deoxy-1-O-diphenoxylphosphoryl-hexopyranoses were generated in situ by a radical 21 migration of the phosphate group. The structures of the reactive rearrangement products were fully elucidated by NMR spectroscopy. Rate constants for this new rearrangement were determined fro a variety of substrates.

  通过磷酸基团的自由基21迁移原位产生了各种2-deoxy-1- O -diphenoxylphosphoryl-heyopyranoses 。反应性重排产物的结构通过NMR光谱充分阐明。对于各种底物，确定了这种新的重排的速率常数。
• Calcium hypophosphite mediated deiodination in water: mechanistic insights and applications in large scale syntheses of <scp>d</scp>-quinovose and <scp>d</scp>-rhamnose
  作者：Zejin Song、Lingkui Meng、Ying Xiao、Xiang Zhao、Jing Fang、Jing Zeng、Qian Wan

  DOI：10.1039/c8gc03851a

  日期：——

  The inorganic calcium hypophosphite was found to be a cheap, non-toxic, water-soluble and environmentally friendly reducing reagent for radical deiodination in water. Thorough mechanism studies revealed that calcium hypophosphite was oxidized to water insoluble calcium phosphite which was the major co-product of the deiodination reaction. Based on this observation, a practical synthesis of rare D-quinovose

  已发现无机次磷酸钙是一种廉价，无毒，水溶性且环保的还原剂，可用于水中的自由基脱碘。深入的机理研究表明，次磷酸钙被氧化为水不溶性亚磷酸钙，这是脱碘反应的主要副产物。基于该观察结果，报道了从廉价且可商购的材料以一百毫摩尔规模实际合成稀有D-奎诺糖和D-鼠李糖的方法。