methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-α-D-rhamnopyranosyl)-α-D-glucopyranoside | 1163254-42-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-α-D-rhamnopyranosyl)-α-D-glucopyranoside
• 英文别名: Bn(-2)[Bn(-3)][Bn(-4)]D-Rha(b1-6)[Bn(-2)][Bn(-3)][Bn(-4)]a-Glc1Me；(2S,3R,4S,5R,6R)-2-methoxy-6-[[(2R,3S,4S,5R,6R)-6-methyl-3,4,5-tris(phenylmethoxy)oxan-2-yl]oxymethyl]-3,4,5-tris(phenylmethoxy)oxane
• CAS: 1163254-42-9
• 化学式: C₅₅H₆₀O₁₀
• 分子量: 881.075
• InChiKey: OZAWEQPEXYIULG-OXSSEZDLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.5
• 重原子数：
  65
• 可旋转键数：
  22
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  92.3
• 氢给体数：
  0
• 氢受体数：
  10

反应信息

• 作为产物：
  描述：

  甲基2,3,4-三-O-苄基-α-D-吡喃葡萄糖苷 、 phenyl-2,3,4-tri-O-benzyl-1-thio-β-D-rhamnose 在 二苯基亚砜 、 2,4,6-三叔丁基嘧啶 、 三氟甲磺酸酐 作用下， 以 二氯甲烷 为溶剂， 反应 0.67h， 生成 methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-α-D-rhamnopyranosyl)-α-D-glucopyranoside 、 methyl 2,3,4-tri-O-benzyl-6-O-(2,3,4-tri-O-benzyl-α-D-rhamnopyranosyl)-α-D-glucopyranoside
  参考文献：
  名称：

  Stereodirecting Effect of the Pyranosyl C-5 Substituent in Glycosylation Reactions

  摘要：

  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.

  DOI：

  10.1021/jo900662v

文献信息

• 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.