methyl 2-O-(β-D-xylopyranosyl)-4-O-(β-D-mannopyranosyl)-α-D-glucopyranoside

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2-O-(β-D-xylopyranosyl)-4-O-(β-D-mannopyranosyl)-α-D-glucopyranoside
• 英文别名: β-D-Xyl-(1->2)-β-D-Man-(1->4)-α-D-Glc-OMe；Xyl(b1-2)Man(b1-4)a-Glc1Me；(2S,3R,4S,5R)-2-[(2S,3S,4S,5S,6R)-2-[(2R,3S,4R,5R,6S)-4,5-dihydroxy-2-(hydroxymethyl)-6-methoxyoxan-3-yl]oxy-4,5-dihydroxy-6-(hydroxymethyl)oxan-3-yl]oxyoxane-3,4,5-triol
• 化学式: C₁₈H₃₂O₁₅
• 分子量: 488.443
• InChiKey: AELLAJNILVAOIR-WMYDBJFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -5.7
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  237
• 氢给体数：
  9
• 氢受体数：
  15

反应信息

• 作为产物：
  描述：

  甲基2,3,6-三-O-苄基-ALPHA-D-吡喃葡萄糖苷 在 palladium on activated charcoal 四氧化锇 、 2,6-二叔丁基-4-甲基吡啶 、 potassium tert-butylate 、 氢气 、 sodium methylate 、 silver trifluoromethanesulfonate 、 N-甲基吗啉氧化物 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 72.0h， 生成 methyl 2-O-(β-D-xylopyranosyl)-4-O-(β-D-mannopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Direct synthesis of β-d-Xyl-(1→2)-β-d-Man-(1→4)-α-d-Glc-OME: a trisaccharide component of the Hyriopsis schlegelii glycosphingolipid

  摘要：

  A synthesis of the target trisaccharide is described in which the key beta-mannosylation is achieved in high yield and selectivity through reaction of the sulfoxide 7 with acceptor 8, mediated with triflic anhydride. The beta-xylosylation was best conducted using tribenzoyl xylopyranosyl bromide and silver triflate. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)00124-5

文献信息

• Stereoselective β‐Mannosylation with 2,6‐Lactone‐bridged Thiomannosyl Donor by Remote Acyl Group Participation
  作者：Huanfang Xu、Long Chen、Qi Zhang、Yingle Feng、Yujia Zu、Yonghai Chai

  DOI：10.1002/asia.201801740

  日期：2019.5.2

  Stereoselective β‐mannosylation has been recognized as one of the greatest challenges of carbohydrate chemistry. Herein, we described a practical method for stereoselective construction of β‐mannosides by using a 2,6‐lactone‐bridged thiomannosyl donor through the remote acyl‐group participation as well as the steric effect of O‐4 substituent. The two effects are enabled through the conversion of a

  立体选择性β-甘露糖基化已被认为是碳水化合物化学的最大挑战之一。在本文中，我们描述了一种通过2,6-内酯桥连的硫代甘露糖基供体通过远程酰基基团参与以及O-4取代基的空间效应来立体选择性构建β-甘露糖苷的方法。通过常规的甘露吡喃糖基4 C 1的转化可以实现这两种作用。构象变成2,6-内酯桥接构象。内酯供体可以很容易地按克级分三个步骤进行制备，β-甘露糖基化反应平稳，对伯，仲和叔醇受体的立体选择性高。此外，该策略已成功应用于天然存在的三糖的合成。
• Direct synthesis of β-mannosides. Synthesis of β-D-xyl-(1→2)-β-D-man-(1→4)-α-D-Glc-OMe: A trisaccharide component of the Hyriopsis schlegelii glycosphingolipid. Formation of an orthoester from a xylopyranosyl sulfoxide
  作者：David Crich、Zongmin Dai

  DOI：10.1016/s0040-4020(98)01202-2

  日期：1999.2

  A concise synthesis of the title trisaccharide is described in which the key β-mannosylation reaction is achieved directly, with high yield and selectivity, by triflic anhydride mediated coupling of S-ethyl2-O-allyl-3-O-benzyl-4,6-O-benzylidene-1-deoxy-1-thia-α-D-mannopyranoside S-(R)-oxide with methyl 2,3,6-tri-O-benzyl-α-D-glucopyranoside. After deallylation of the so-formed disaccharide, β-xylopyranosylation

  描述了标题三糖的简明合成，其中通过三氟乙酸酐介导的S-乙基2- O-烯丙基-3- O-苄基-4,6的偶联直接直接以高收率和选择性实现关键的β-甘露糖基化反应。- ø -亚苄基-1-脱氧-1-硫杂α-d-D-吡喃甘露糖苷小号- （[R ）-氧化物与甲基2,3,6-三- ö苄基α-d-D-吡喃葡萄糖苷。如此形成的二糖脱甲酰化后，通过与由三氟甲磺酸银活化的α-三-O-苯甲酰基木吡喃糖基溴的反应，引起β-木吡喃糖基化。尝试用S -phenyl2,3,4-tri-将环己醇木糖基化Ô苯甲酰基1-脱氧-1-硫代β-d-D-吡喃木糖苷小号氧化物，由三氟甲磺酸酐活化，并与三氟甲磺酸benzenesulfenyl的存在相应的硫糖苷既导致形成的原酸酯，而不是预期的β -木糖甙。用四氯化锡处理该原酸酯会促进其重排为β-木糖苷。讨论了三-O-苯甲酰基-β-吡喃吡喃糖苷的构象和构型分配。
• Practical Synthesis of .beta.-D-Xyl-(1.fwdarw.2)-.beta.-D-Man-(1.fwdarw.4)-.alpha.-D-Glc-OMe, a Trisaccharide Component of the Hyriopsis schlegelii Glycosphingolipid
  作者：Frieder W. Lichtenthaler、Thomas Schneider-Adams、Stefan Immel

  DOI：10.1021/jo00101a036

  日期：1994.11

  By employing the readily accessible (preceding paper in this issue) 3,4,6-tri-O-benzyl-alpha-D-arabino-hexosyl bromide (1) as an indirect, beta-specific mannosyl donor, a practical three-step synthesis was elaborated for methyl xylosyl-beta(1-->2)-mannosyl-beta(1-->4)-glucoside (11), a trisaccharide component of Hyriopsis schlegelii ceramide oligosaccharides. Key steps were the silver aluminosilicate-induced, beta-specific glycosidation of 1 with methyl 2,3,6-tri-O-benzyl-alpha-D-glucoside and the silver triflate-promoted beta-xylosylation with 2,3,4-tri-O-benzoyl-alpha-D-xylosyl bromide. The overall yield amounted to a satisfactory 47%.
• Direct synthesis of β-d-Xyl-(1→2)-β-d-Man-(1→4)-α-d-Glc-OME: a trisaccharide component of the Hyriopsis schlegelii glycosphingolipid
  作者：David Crich、Zongmin Dai

  DOI：10.1016/s0040-4039(98)00124-5

  日期：1998.3

  A synthesis of the target trisaccharide is described in which the key beta-mannosylation is achieved in high yield and selectivity through reaction of the sulfoxide 7 with acceptor 8, mediated with triflic anhydride. The beta-xylosylation was best conducted using tribenzoyl xylopyranosyl bromide and silver triflate. (C) 1998 Elsevier Science Ltd. All rights reserved.