(2S,3S,4S,5R,6S)-3,4,5-Tris-benzyloxy-6-((2R,3R,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-ylmethoxy)-tetrahydro-pyran-2-carboxylic acid methyl ester | 75336-67-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,3S,4S,5R,6S)-3,4,5-Tris-benzyloxy-6-((2R,3R,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-ylmethoxy)-tetrahydro-pyran-2-carboxylic acid methyl ester
• CAS: 75336-67-3
• 化学式: C₅₆H₆₀O₁₂
• 分子量: 925.085
• InChiKey: KGVMUXZIXGUOEL-WPITZJJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  68.0
• 可旋转键数：
  23.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  118.6
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为产物：
  描述：

  methyl 2,3,4-tri-O-benzyl-α-D-glucopyranuronate 在 silver perchlorate 、 三溴化磷 、 乙腈 作用下， 反应 0.67h， 生成 (2S,3S,4S,5R,6S)-3,4,5-Tris-benzyloxy-6-((2R,3R,4S,5R,6S)-3,4,5-tris-benzyloxy-6-methoxy-tetrahydro-pyran-2-ylmethoxy)-tetrahydro-pyran-2-carboxylic acid methyl ester
  参考文献：
  名称：

  Stereoselective glycosidations of uronic acids

  摘要：

  DOI：

  10.1016/s0040-4039(00)92735-7

文献信息

• A “Traceless” Directing Group Enables Catalytic S_<i>N</i>2 Glycosylation toward 1,2-<i>cis</i>-Glycopyranosides
  作者：Xu Ma、Zhitong Zheng、Yue Fu、Xijun Zhu、Peng Liu、Liming Zhang

  DOI：10.1021/jacs.1c04584

  日期：2021.8.11

  Generally applicable and stereoselective formation of 1,2-cis-glycopyranosidic linkage remains a long sought after yet unmet goal in carbohydrate chemistry. This work advances a strategy to this challenge via stereoinversion at the anomeric position of 1,2-trans glycosyl ester donors. This SN2 glycosylation is enabled under gold catalysis by an oxazole-based directing group optimally tethered to a

  1,2-顺式-吡喃糖苷键的普遍适用和立体选择性形成仍然是碳水化合物化学中长期追求但尚未实现的目标。这项工作通过在 1,2-反式糖基酯供体的异头位置上的立体倒置推进了应对这一挑战的策略。这种 S N 2 糖基化是在金催化下通过以恶唑为基础的导向基团实现的，该导向基团最佳地束缚在离去基团上，并在温和的催化条件下以大多数优异的产率和良好的选择性实现。该策略也适用于寡糖的合成。
• A rapid and efficient synthesis of 1,2-trans-β-linked glycosides via benzyl- or benzoyl-protected glycopyranosyl phosphates
  作者：Shun-ichi Hashimoto、Takeshi Honda、Shiro Ikegami

  DOI：10.1039/c39890000685

  日期：——

  A highly stereocontrolled construction of 1,2-trans-β-glycosidic linkage with or without neighbouring-group participation has been achieved using benzyl- or benzoyl-protected glycopyranosyl phosphates as glycosyl donors in the presence of trimethylsilyl triflate (TMSOTf).

  在存在三甲基甲硅烷基三氟甲磺酸酯（TMSOTf）的情况下，使用苄基或苯甲酰基保护的吡喃葡萄糖基磷酸酯作为糖基供体，已经实现了具有或不具有邻基参与的1,2-反式-β-糖苷键的高度立体控制的构建。
• Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions
  作者：Jasper Dinkelaar、Ana Rae de Jong、Robert van Meer、Mark Somers、Gerrit Lodder、Herman S. Overkleeft、Jeroen D. C. Codée、Gijsbert A. van der Marel

  DOI：10.1021/jo900662v

  日期：2009.7.17

  The stereodirecting effect of the glycosyl C-5 substituent has been investigated in a series of D-pyranosyl thioglycoside donors and related to their preferred positions in the intermediate H-3(4) and H-4(3) half-chair oxacarbenium ions. Computational studies showed that an axially positioned C-5 carboxylate ester can stabilize the (3)H4 half-chair oxacarbenium ion conformer by donating electron densit from its carbonyl function into the electron-poor oxacarbenium ion functionality. A similar stabilization can be achieved by a C-5 benzyloxyrnethyl group, but,the magnitude of this stabilization is significantly smaller than for the C-5 carboxylate ester. As a result, the preference of the C-5 benzyloxymethyl to occupy an axial position in the half-chair oxacarbenium ions is much reduced compared to the C-5 carboxylate ester. To minimize steric interactions, a C-5 methyl group prefers to adopt an equatorial position and therefore favors the H-4(3) half-chair oxacarbenium ion. When all pyranosyl substituents occupy their favored position in one of the two intermediate half-chair oxacarbenium ions, highly stereoselective glycosylations can be achieved as revealed by the excellent beta-selectivity of mannuronate esters and alpha-selectivity of 6-deoxygulosides.