ethyl (3-O-benzyl-4,6-O-isopropylidene-β-D-arabino-hexopyranosyl-2-ulose)-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside | 322479-10-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: ethyl (3-O-benzyl-4,6-O-isopropylidene-β-D-arabino-hexopyranosyl-2-ulose)-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside
• CAS: 322479-10-7
• 化学式: C₄₆H₄₉NO₁₁S
• 分子量: 823.961
• InChiKey: ROSMVONNKOSCJB-ACVLBNNOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.35
• 重原子数：
  59.0
• 可旋转键数：
  15.0
• 环数：
  8.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  128.29
• 氢给体数：
  0.0
• 氢受体数：
  12.0

反应信息

• 作为反应物：
  描述：

  ethyl (3-O-benzyl-4,6-O-isopropylidene-β-D-arabino-hexopyranosyl-2-ulose)-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside 在 acetoxydimethylsulfonium acetate 、 tetrabutylammonium borohydride 作用下， 以 四氢呋喃 、 二甲基亚砜 为溶剂， 反应 0.33h， 以80%的产率得到ethyl (3-O-benzyl-4,6-O-isopropylidene-β-D-mannopyranosyl)-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  New Factors Governing Stereoselectivity in Borohydride Reductions ofβ-D-Glycoside-2-uloses − The Peculiar Effect of “Activated” DMSO

  摘要：

  Comparative evaluation of the manno/gluco ratios obtained in the conventional reductions of beta -D-glucoside-2-uloses (1-4, 13 and 14) reveals the influence of the substitution pattern: the presence of a 4,6-O-acetal function results in lower stereoselectivity in the monosaccharide-uloside cases and low stereoselectivity in the disaccharide-uloside cases, while the absence of a 4,6-O-acetal group provides distinctly higher stereoselectivity. The 3-O-benzyl and 3-O-allyl ethers vicinal to the carbonyl to be reduced have a similar influence on the steric outcome of the carbonyl reduction. A peculiar effect of acetoxydimethylsulfonium acetate ("activated" DMSO) was observed. In all cases, its presence strongly increased the manno-selectivity of the reduction. A simple, preparatively expedient, commonly suitable protocol has been elaborated for achieving high manno-selectivities and, hence, satisfactory yields.

  DOI：

  10.1002/1099-0690(200012)2000:23<3931::aid-ejoc3931>3.0.co;2-w
• 作为产物：
  描述：

  ethyl 3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside 在 sodium methylate 、 silver trifluoromethanesulfonate 、 乙酸酐 、 对甲苯磺酸 、 二甲基亚砜 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 17.5h， 生成 ethyl (3-O-benzyl-4,6-O-isopropylidene-β-D-arabino-hexopyranosyl-2-ulose)-(1->4)-3,6-di-O-benzyl-2-deoxy-2-phthalimido-1-thio-β-D-glucopyranoside
  参考文献：
  名称：

  New Factors Governing Stereoselectivity in Borohydride Reductions ofβ-D-Glycoside-2-uloses − The Peculiar Effect of “Activated” DMSO

  摘要：

  Comparative evaluation of the manno/gluco ratios obtained in the conventional reductions of beta -D-glucoside-2-uloses (1-4, 13 and 14) reveals the influence of the substitution pattern: the presence of a 4,6-O-acetal function results in lower stereoselectivity in the monosaccharide-uloside cases and low stereoselectivity in the disaccharide-uloside cases, while the absence of a 4,6-O-acetal group provides distinctly higher stereoselectivity. The 3-O-benzyl and 3-O-allyl ethers vicinal to the carbonyl to be reduced have a similar influence on the steric outcome of the carbonyl reduction. A peculiar effect of acetoxydimethylsulfonium acetate ("activated" DMSO) was observed. In all cases, its presence strongly increased the manno-selectivity of the reduction. A simple, preparatively expedient, commonly suitable protocol has been elaborated for achieving high manno-selectivities and, hence, satisfactory yields.

  DOI：

  10.1002/1099-0690(200012)2000:23<3931::aid-ejoc3931>3.0.co;2-w