(4aR,6R,8S,8aR)-8-Allyloxy-6-methoxy-2,2-dimethyl-tetrahydro-pyrano[3,2-d][1,3]dioxin-7-one | 322479-09-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡喃二恶英
• 英文名称: (4aR,6R,8S,8aR)-8-Allyloxy-6-methoxy-2,2-dimethyl-tetrahydro-pyrano[3,2-d][1,3]dioxin-7-one
• 英文别名: (4aR,6R,8S,8aR)-6-methoxy-2,2-dimethyl-8-prop-2-enoxy-4,4a,8,8a-tetrahydropyrano[3,2-d][1,3]dioxin-7-one
• CAS: 322479-09-4
• 化学式: C₁₃H₂₀O₆
• 分子量: 272.298
• InChiKey: UFNZUFBKJXJSBX-HJQYOEGKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  63.2
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (4aR,6R,8S,8aR)-8-Allyloxy-6-methoxy-2,2-dimethyl-tetrahydro-pyrano[3,2-d][1,3]dioxin-7-one 在 tetrabutylammonium borohydride 作用下， 以 四氢呋喃 为溶剂， 以93%的产率得到methyl 3-O-allyl-4,6-O-isopropylidene-β-D-mannopyranoside
  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：

  methyl 3-O-allyl-β-D-glucopyranoside 在 乙酸酐 、 对甲苯磺酸 、 二甲基亚砜 作用下， 反应 16.33h， 生成 (4aR,6R,8S,8aR)-8-Allyloxy-6-methoxy-2,2-dimethyl-tetrahydro-pyrano[3,2-d][1,3]dioxin-7-one
  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

文献信息

• New Factors Governing Stereoselectivity in Borohydride Reductions ofβ-D-Glycoside-2-uloses − The Peculiar Effect of “Activated” DMSO
  作者：János Kerékgyártó、János Rákó、Károly Ágoston、Gyöngyi Gyémánt、Zoltán Szurmai

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

  日期：2000.12

  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.