ethyl 3,4-di-O-benzyl-1-thio-α-D-mannopyranoside | 496812-01-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl 3,4-di-O-benzyl-1-thio-α-D-mannopyranoside
• 英文别名: (2R,3S,4R,5R,6R)-2-ethylsulfanyl-6-(hydroxymethyl)-4,5-bis(phenylmethoxy)oxan-3-ol
• CAS: 496812-01-2
• 化学式: C₂₂H₂₈O₅S
• 分子量: 404.527
• InChiKey: LSOFHCQWWBITMC-PVIWCNJMSA-N

物化性质

• 沸点：
  578.1±50.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  28
• 可旋转键数：
  9
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  93.4
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  ethyl 3,4-di-O-benzyl-1-thio-α-D-mannopyranoside 在 吡啶 、 N-碘代丁二酰亚胺 、 三氟甲磺酸 、 sodium methylate 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 生成 (2R,3S,4R,5R,6R)-6-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-2-[(2S,3S,4S,5R,6R)-2-methoxy-4,5-bis(phenylmethoxy)-6-(phenylmethoxymethyl)oxan-3-yl]oxy-4,5-bis(phenylmethoxy)oxan-3-ol
  参考文献：
  名称：

  Synthesis of a peptidyldimannosyl phosphate: fragment of the variant-specific surface glycoprotein membrane anchor from trypanosoma brucei

  摘要：

  Condensation of protected beta-benzyl-aspartate 4 with 2-amino-ethanol, subsequent deprotection of the amino function and coupling with N',N'-di-benzylocarbonyl-lysine (7) afforded the peptidyl alcohol 8. Glycosylation of methyl 3,4,6 tri-O-benzyl-alpha-D-mannopyranoside (11) by ethyl 2,6-di-O-benzoyl-3,4-di-O-benzyl-1-thio-alpha-D-mannopyranoside (14) gave, after debenzoylation and protection of the 2'-hydroxyl function, the suitably protected dimannoside 21. Phosphitylation of 21 with benzyloxy-bis-(N, N-diisopropylamino)phosphine (18) followed by the addition of 8 gave, after oxidation and subsequent hydrogenolysis of the benzyl groups, the title compound in a good yield.

  DOI：

  10.1016/0040-4039(91)80242-x
• 作为产物：
  描述：

  1,2,6-三-O-乙酰基-3,4-二-O-苄基吡喃己糖 在 三氟甲磺酸三甲基硅酯 、 sodium methylate 作用下， 以 甲醇 、 二氯甲烷 、 1,2-二氯乙烷 为溶剂， 生成 ethyl 3,4-di-O-benzyl-1-thio-α-D-mannopyranoside
  参考文献：
  名称：

  Synthesis of a peptidyldimannosyl phosphate: fragment of the variant-specific surface glycoprotein membrane anchor from trypanosoma brucei

  摘要：

  Condensation of protected beta-benzyl-aspartate 4 with 2-amino-ethanol, subsequent deprotection of the amino function and coupling with N',N'-di-benzylocarbonyl-lysine (7) afforded the peptidyl alcohol 8. Glycosylation of methyl 3,4,6 tri-O-benzyl-alpha-D-mannopyranoside (11) by ethyl 2,6-di-O-benzoyl-3,4-di-O-benzyl-1-thio-alpha-D-mannopyranoside (14) gave, after debenzoylation and protection of the 2'-hydroxyl function, the suitably protected dimannoside 21. Phosphitylation of 21 with benzyloxy-bis-(N, N-diisopropylamino)phosphine (18) followed by the addition of 8 gave, after oxidation and subsequent hydrogenolysis of the benzyl groups, the title compound in a good yield.

  DOI：

  10.1016/0040-4039(91)80242-x

文献信息

• SmI₂/Water/Amine Mediates Cleavage of Allyl Ether Protected Alcohols:  Application in Carbohydrate Synthesis and Mechanistic Considerations
  作者：Anders Dahlén、Andreas Sundgren、Martina Lahmann、Stefan Oscarson、Göran Hilmersson

  DOI：10.1021/ol0354831

  日期：2003.10.1

  [reaction: see text]. SmI2/H2O/amine provides selective cleavage of unsubstituted allyl ethers in good to excellent yields. This method is therefore useful in deprotection of alcohols and carbohydrates.

  [反应：请参见文字]。SmI2 / H2O /胺可很好地至优异的收率选择性裂解未取代的烯丙基醚。因此，该方法可用于醇和碳水化合物的脱保护。
• Preparation of 1-Thio Uronic Acid Lactones and Their Use in Oligosaccharide Synthesis
  作者：Leendert J. van den Bos、Remy E. J. N. Litjens、Richard J. B. H. N. van den Berg、Herman S. Overkleeft、Gijsbert A. van der Marel

  DOI：10.1021/ol050491y

  日期：2005.5.1

  TEMPO/BAIB-mediated oxidation of 2,6- and 3,6-dihydroxy 1-thio glycopyranosides to the corresponding 1-thio uronic acid lactones is described. These locked 1-thio glycuronides can directly be used as donors in glycosidation reactions using the Ph(2)SO/Tf(2)O reagent system. Alternatively, selective opening of the lactone bridge liberates a hydroxyl function for ensuing glycosylations.

  描述了由化学和区域选择性的TEMPO / BAIB介导的2,6-和3,6-二羟基1-硫代糖吡喃糖苷氧化为相应的1-硫代糖醛酸内酯。使用Ph（2）SO / Tf（2）O试剂系统，可以将这些锁定的1-硫代乙二醛糖醛酸酯直接用作糖苷化反应中的供体。可替代地，内酯桥的选择性开放释放了用于随后糖基化的羟基功能。
• β-Stereoselective Mannosylation Using 2,6-Lactones
  作者：Yusuke Hashimoto、Saki Tanikawa、Ryota Saito、Kaname Sasaki

  DOI：10.1021/jacs.6b08874

  日期：2016.11.16

  the competing SN1 reaction, affording β-glycosides with stereoinversion via SN2(-like) mechanisms. Glycosyl trichloroacetimidates are particularly efficient when activated by a combined catalyst of AuCl3 and 3,5-bis(trifluoromethyl)phenyl thiourea. In addition, the product stereoselectivity was highly dependent on the concentration of the reaction. Moreover, even when the reaction proceeds via an SN1

  描述了使用带有 2,6-内酯部分的供体进行的 β-立体选择性甘露糖基化。通常，糖基化是醇亲核试剂与在异头位置含有离去基团的糖部分之间的亲核取代反应。由于立体电子效应，反应倾向于通过SN1机制进行以提供α-糖苷。我们发现引入 2,6-内酯桥可以规避竞争性 SN1 反应，通过 SN2(-like) 机制提供具有立体反转功能的 β-糖苷。当用 AuCl3 和 3,5-双（三氟甲基）苯基硫脲的组合催化剂活化时，糖基三氯乙酰亚胺酯特别有效。此外，产物立体选择性高度依赖于反应的浓度。此外，即使反应通过 SN1 机制进行，相应的糖基阳离子似乎在空间上呈现 β 导向性质。总的来说，2,6-内酯是实现β-甘露糖基化的有希望的结构。
• Automated glycan assembly of arabinomannan oligosaccharides from <i>Mycobacterium tuberculosis</i>
  作者：Alonso Pardo-Vargas、Priya Bharate、Martina Delbianco、Peter H Seeberger

  DOI：10.3762/bjoc.15.288

  日期：——

  Automated glycan assembly (AGA) was employed to prepare the core structure of AM from MTB, containing α-(1,6)-Man, α-(1,5)-Ara, and α-(1,2)-Man linkages. The introduction of a capping step after each glycosylation and further optimized reaction conditions allowed for the synthesis of a series of oligosaccharides, ranging from hexa- to branched dodecasaccharides.

  阿拉伯甘露聚糖（AM）多糖是结核分枝杆菌（MTB）感染的临床生物标志物，因为它们在与宿主细胞相互作用和干扰巨噬细胞活化中发挥作用。定义的AM寡糖的集合可以帮助提高对这些多糖的了解，并开发新的治疗和诊断剂。使用自动聚糖组装（AGA）从MTB制备AM的核心结构，该结构包含α-（1,6）-Man，α-（1,5）-Ara和α-（1,2）-Man键。在每次糖基化和进一步优化的反应条件后引入封端步骤，可以合成一系列低聚糖，范围从六糖到支链十二糖。
• Synthesis of a polyphosphorylated GPI-anchor core structure
  作者：Martina Lahmann、Per J Garegg、Peter Konradsson、Stefan Oscarson

  DOI：10.1139/v02-160

  日期：2002.8.1

  Using a linear assembly approach a highly differentially protected derivative of the common GPI-anchor core structure (α-D-Man-(1[Formula: see text]6)-α-D-Man-(1[Formula: see text]2)-α-D-Man-(1[Formula: see text]4)-α-D-GlcNH₂-(1[Formula: see text]6)-D-myo-inositol) has been synthesized. All mannose donors were prepared from a common thioglycoside precursor (1), and coupled to GlcN₃-myo-inositol acceptor 5 in a linear five-step glycosylation–deprotection sequence in 49% overall yield, to give the key intermediate 10, with orthogonal temporary protecting groups at the 6'', 2'', 6', and 2 positions of the trimannoside motif and at the 1 and 2 positions of the inositol part. Consecutive removal of the temporary protecting groups in the trimannoside moiety followed by phosphorylation, gave a tetraphosphosphate derivative in 60% overall yield. Removal of a camphor acetal afforded a 1,2-inositol diol, which was converted to a 1,2-cyclic phosphate using commercial methyl dichlorophosphate ([Formula: see text]17, 95%). One-step deprotection using sodium in liquid ammonia afforded the target polyphosphorylated core structure 18 (60%), which will be tested for metabolic insulin action.Key words: glycophosphatidylinositols, linear synthesis, glycosylations, inositolphosphoglycans, IPG.

  使用线性组装方法合成了常见GPI锚核心结构（α-D-Man-(1[Formula: see text]6)-α-D-Man-(1[Formula: see text]2)-α-D-Man-(1[Formula: see text]4)-α-D-GlcNH₂-(1[Formula: see text]6)-D-myo-inositol）的高度差异保护衍生物。所有甘露糖供体均由共同的硫代糖苷前体（1）制备而成，并在线性五步糖基化-去保护序列中与GlcN₃-myo-inositol受体5偶联，以49％的总产率给出关键中间体10，在三甘露糖基团的6''，2''，6'和2位及肌醇部分的1和2位具有正交临时保护基。连续去除三甘露糖基团中的临时保护基，随后进行磷酸化，以60％的总产率给出四磷酸盐衍生物。去除蒎烷缩醛后得到1,2-肌醇二醇，使用商业甲基二氯膦（[Formula: see text]17，95％）将其转化为1,2-环磷酸酯。使用液氨钠进行一步去保护，以60％的产率得到目标多磷酸化核心结构18，将用于测试代谢胰岛素作用。关键词：糖脂磷酸肌醇，线性合成，糖基化，肌醇磷酸糖，IPG。