4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide | 74517-02-5

• 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: 4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide
• 英文别名: [(3aR,4S,6S,7S,7aR)-4-bromo-6-methyl-2-oxo-4,6,7,7a-tetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl] acetate
• CAS: 74517-02-5
• 化学式: C₉H₁₁BrO₆
• 分子量: 295.087
• InChiKey: GGWOTVHIKZMVLZ-IMSDGWMTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  71.1
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide 在 4 A molecular sieve 、 sodium methylate 、 silver(l) oxide 作用下， 反应 33.0h， 生成 6-O-β-L-rhamnopyranosyl-D-glucopyranose
  参考文献：
  名称：

  β-1-鼠李糖吡喃糖苷的合成及13C-nmr光谱

  摘要：

  摘要基于4的使用，合成甲基β-1-鼠李糖吡喃糖苷，6-O-β-鼠李糖吡喃糖基-d-葡萄糖和-d-半乳糖和4-O-β-鼠李糖吡喃糖基-l-鼠李糖。描述了-O-乙酰基-2，3-O-羰基-α-1-鼠李糖基吡喃糖基溴化物作为糖基化剂。将β-1-鼠李糖苷的13 Cn.mr光谱与相应的α端基异构体的光谱进行比较。

  DOI：

  10.1016/s0008-6215(00)85553-6
• 作为产物：
  描述：

  phenyl 4-O-acetyl-1-thio-α-L-rhamnopyranoside 在 吡啶 、 溴 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 3.0h， 生成 4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide
  参考文献：
  名称：

  The 3,4-O-Carbonate Protecting Group as a β-Directing Group in Rhamnopyranosylation in Both Homogeneous and Heterogeneous Glycosylations As Compared to the Chameleon-like 2,3-O-Carbonates

  摘要：

  It is demonstrated that the beta-selectivity observed in the insoluble silver salt mediated couplings of 2,3-O-carbonate-protected rhamnosyl bromides is uniquely due to the heterogeneous nature of the reaction. In homogeneous solution these same donors are alpha-selective, a fact that is attributed to the half-chair conformation of these substances which reduces the energy barrier to oxacarbenium ion formation. It is suggested that the 2,3-O-carbonate group be dubbed torsionally arming in the manno- and rhamnopyranose series. When the carbonate group is removed to the 3,4-O-position a beta-selective system is formed, in both homogeneous and heterogeneous conditions, and it is demonstrated that this selectivity arises from the combination of the electron-withdrawing nature of the carbonate and its inability to take part in neighboring participation.

  DOI：

  10.1021/jo035003j

文献信息

• Synthesis of apiose-containing oligosaccharide fragments of the plant cell wall: fragments of rhamnogalacturonan-II side chains A and B, and apiogalacturonan
  作者：Sergey A. Nepogodiev、Margherita Fais、David L. Hughes、Robert A. Field

  DOI：10.1039/c1ob05587a

  日期：——

  Fragments of pectic polysaccharides rhamnogalacturonan-II (RG-II) and apiogalacturonan were synthesised using p-tolylthio apiofuranoside derivatives as key building blocks. Apiofuranose thioglycosides can be conveniently prepared by cyclization of the corresponding dithioacetals possessing a 2,3-O-isopropylidene group, which is required for preservation of the correct (3R) configuration of the apiofuranose

  果胶多糖rhamnogalacturonan-II (RG-II) 和apiogalacturonan 的片段是使用p- tolylthio apiofuranoside 衍生物作为关键构建块合成的。硫代呋喃糖苷可以通过相应的具有 2,3- O-异亚丙基的二硫代缩醛的环化来方便地制备，这是保持apiofuranose 环的正确 ( 3R ) 构型所必需的。这种保护基团在吡呋喃糖衍生物中的显着稳定性需要用更具反应性的保护基团替换，例如用于合成三糖 β-Rha p -(1→3')-β-Api f -的亚苄基缩醛- (1→2)-α-GalA p-OMe。该三糖的受保护前体的 X 射线晶体结构已被阐明。
• Synthèses du β-<scp>L</scp>-rhamnopyranoside d'hordénine et d'acylgluco-<scp>L</scp>-rhamnopyranoses peracétylés
  作者：Nadia Boughandjioua、Lin Rui Chao、Alexios-Leandros Skaltsounis、Elisabeth Seguin、François Tillequin、Michel Koch

  DOI：10.1139/v92-245

  日期：1992.7.1

  The stereoselective synthesis of hordenine β-L-rhamnopyranoside (3) was achieved using 4-O-acetyl-2,3-O-carbonyl-α-L-rhamnopyranosyl bromide (14) as key intermediate. The regiospecific syntheses of the peracetyl derivatives of (E)-O-(6-O-cinnamoyl-β-D-glucopyranosyl)-(1 → 2)-, (1 → 3)-, and (1 → 4)-α-L-rhamnopyranoses and of their 4-acetoxycinnamoyl counterparts were achieved through the use of various types of rhamnose-derived intermediates, i.e., 1,2-O-orthoester for the (1 → 2) series, 2,3-O-orthoester for the (1 → 3) series, and 2,3-O-isopropylidene for the (1 → 4) series.

  使用4-O-乙酰基-2,3-O-羰基-α-L-鼠李糖基溴化物（14）作为关键中间体，实现了异构选择性合成鼠李糖基β-L-喝荡碱苷（3）。通过使用不同类型的鼠李糖衍生中间体，即1,2-O-正交酯用于（1→2）系列，2,3-O-正交酯用于（1→3）系列，以及2,3-O-异丙基亚甲基用于（1→4）系列，实现了（E）-O-(6-O-肉桂酰基-β-D-葡萄糖基)-(1→2)-、(1→3)-和(1→4)-α-L-鼠李糖苷的特定区域合成以及它们的4-乙酰氧基肉桂酰基对应物的合成。
• Synthesis of an apiose-containing disaccharide fragment of rhamnogalacturonan-II and some analogues
  作者：Anne-Laure Chauvin、Sergey A. Nepogodiev、Robert A. Field

  DOI：10.1016/j.carres.2003.09.031

  日期：2004.1

  3-O-isopropylidene-beta-D-erythrofuranoside and methyl 2,3-O-isopropylidene-beta-D-ribofuranoside was achieved using 4-O-acetyl-2,3-O-carbonyl-alpha-L-rhamnopyranosyl bromide and Ag2O as a promoter. Deprotected disaccharides beta-L-Rhap-(1-->3')-beta-D-Apif-OMe and beta-L-Rhap-(1-->3')-beta-D-Ribf-OMe were compared to their alpha-rhamnosyl isomers which were prepared using conventional Helferich glycosylation.

  使用4-O-乙酰基-2可实现甲基2-C-羟甲基-2,3-O-异亚丙基-β-D-呋喃呋喃糖苷和甲基2,3-O-异亚丙基-β-D-呋喃呋喃糖苷的β-鼠李糖基化反应， 3-O-羰基-α-L-鼠李糖基溴化物和Ag2O作为促进剂。将脱保护的二糖β-L-Rhap-（1-> 3'）-β-D-Apif-OMe和β-L-Rhap-（1-> 3'）-β-D-Ribf-OMe与它们的α-鼠李糖基异构体，它们是用常规的Helferich糖基化制备的。
• Synthesis of fluorescently labelled rhamnosides: probes for the evaluation of rhamnogalacturonan II biosynthetic enzymes
  作者：Efthymia Prifti、Stephan Goetz、Sergey A. Nepogodiev、Robert A. Field

  DOI：10.1016/j.carres.2011.03.039

  日期：2011.9

  Three fluorescently labelled saccharides 10-12, representing structures found in pectic glycan rhamnogalacturonan II (RG-II), were synthesised by chemical glycosylation of O-6 of diacetone-D-galactose followed by deprotection and reductive amination with amino-substituted fluorophore APTS. This convenient method installs a common aminogalactitol-based tether in order to preserve the integrity of the reducing end of specific carbohydrates of interest. APTS-labelled glycans prepared in this manner were purified by carbohydrate gel electrophoresis and subjected to capillary electrophoresis analysis, as a basis for the subsequent development of high sensitivity assays for RG-II-active enzymes. (C) 2011 Elsevier Ltd. All rights reserved.
• Kamiya, Shintaro; Esaki, Sachiko; Shiba, Naoko, Agricultural and Biological Chemistry, 1987, vol. 51, # 4, p. 1195 - 1198
  作者：Kamiya, Shintaro、Esaki, Sachiko、Shiba, Naoko

  DOI：——

  日期：——