methyl (2S,3S,4S,5R,6R)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-3,4,5-tris(phenylmethoxy)oxane-2-carboxylate | 75336-69-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (2S,3S,4S,5R,6R)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-3,4,5-tris(phenylmethoxy)oxane-2-carboxylate
• CAS: 75336-69-5
• 化学式: C₅₆H₆₀O₁₂
• 分子量: 925.085
• InChiKey: KGVMUXZIXGUOEL-PVMMJXGQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  68
• 可旋转键数：
  24
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.34
• 拓扑面积：
  119
• 氢给体数：
  0
• 氢受体数：
  12

反应信息

• 作为产物：
  描述：

  methyl 2,3,4-tris-O-(phenylmethyl)-α-D-glucopyranuorate 在 三氟化硼乙醚 sodium hydride 作用下， 以 二氯甲烷 为溶剂， 反应 2.25h， 生成 methyl (2S,3S,4S,5R,6R)-6-[[(2R,3R,4S,5R,6S)-6-methoxy-3,4,5-tris(phenylmethoxy)oxan-2-yl]methoxy]-3,4,5-tris(phenylmethoxy)oxane-2-carboxylate
  参考文献：
  名称：

  Einfache Synthese von β-D-Glucopyranosyluronaten

  摘要：

  DOI：

  10.1055/s-1981-29632

文献信息

• An extremely mild and stereocontrolled construction of 1,2-trans-β-glycosidic linkages capitalizing on benzyl-protected glycopyranosyl diethyl phosphites as glycosyl donors
  作者：Shun-ichi Hashimoto、Kazuhiro Umeo、Ai Sano、Nobuhide Watanabe、Makoto Nakajima、Shiro Ikegami

  DOI：10.1016/0040-4039(95)00263-c

  日期：1995.3

  neighboring group participation has been developed by using benzyl-protected glycopyranosyl diethyl phosphites as glycosyl donors and boron trifluoride etherate as a promoter. The present method exhibits the highest level of 1,2-trans-β-selectivity known to date for glycosidations with a non-participating group on O-2.

  已经通过使用苄基保护的亚磷酸吡喃葡萄糖基二乙基亚磷酸酯作为糖基供体和三氟化硼醚化物作为促进剂，开发了没有相邻基团参与的高度立体控制的1,2-反式-β-糖苷化反应。本方法展现出迄今已知的对于O-2上具有非参与基团的糖苷化的最高水平的1，2-反式-β-选择性。
• 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.
• Stereoselective glycosidations of uronic acids
  作者：Richard R. Schmidt、Ernst Rücker

  DOI：10.1016/s0040-4039(00)92735-7

  日期：——