(3aR,5R,6R,6aR)-6-Allyl-6-methoxy-2,2-dimethyl-5-vinyl-tetrahydro-furo[2,3-d][1,3]dioxole | 541507-91-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,5R,6R,6aR)-6-Allyl-6-methoxy-2,2-dimethyl-5-vinyl-tetrahydro-furo[2,3-d][1,3]dioxole
• 英文别名: (3aR,5R,6R,6aR)-5-ethenyl-6-methoxy-2,2-dimethyl-6-prop-2-enyl-5,6a-dihydro-3aH-furo[2,3-d][1,3]dioxole
• CAS: 541507-91-9
• 化学式: C₁₃H₂₀O₄
• 分子量: 240.299
• InChiKey: WDKMKZIBZSIKHG-LSCVPOLPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3aR,5R,6R,6aR)-6-Allyl-6-methoxy-2,2-dimethyl-5-vinyl-tetrahydro-furo[2,3-d][1,3]dioxole 在 三氟甲烷磺酸亚铜(I)苯联合体 (2:1) 作用下， 以 乙醚 为溶剂， 反应 3.5h， 以73%的产率得到cis-syn-cis-4α,5α-O-isopropylidene-6α-methoxy-3-oxatricyclo[3.2.0.0^2,6]decane
  参考文献：
  名称：

  Intramolecular [2 + 2] Photocycloaddition of Alkenes Incorporated in a Carbohydrate Template. Synthesis of Enantiopure Bicyclo[3.2.0]heptanes and -[6.3.0]undecanes

  摘要：

  Intramolecular [2 + 2] photocycloaddition of alkenes with a furano sugar placed between them have been investigated under both copper(l)-catalyzed and sensitized conditions. The copper(l)catalyzed photocycloaddition of the dienes 4a, 4b, and 4c led to unexpected formation of the thermodynamically less stable cis-syn-cis 4-5-5 tricyclic adducts 5a, 5b, and 5c, respectively. The sensitized photocycloaddition of the diene 14 also gave the cis-syn-cis adduct 15 showing that the copper(I) catalyst does not have any influence on the stereochemical course through coordination with the anomeric ring oxygen of the furano sugar. The identical stereochemical course observed under both catalyzed and sensitized photoaddition reactions have been attributed to be of steric origin. Bis(dienes) 25a and 25b, which gave an intractable mixture on copper(l)-catalyzed irradiation, underwent smooth photocycloaddition in the presence of benzophenone, and the resulting 1,2-divinyl cyclobutanes underwent spontaneous [3.3]-rearrangement at room temperature to produce bicyclo[6.3.0]undecanes 30a and 30b, respectively. This investigation provides an approach for the construction of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes.

  DOI：

  10.1021/jo026920c
• 作为产物：
  描述：

  1:2,5:6-di-O-isopropylidene-3-C-(2'-propenyl)-α-D-allofuranose 在 咪唑 、 碘 、 sodium hydride 、 溶剂黄146 、 三苯基膦 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 甲苯 为溶剂， 反应 16.0h， 生成 (3aR,5R,6R,6aR)-6-Allyl-6-methoxy-2,2-dimethyl-5-vinyl-tetrahydro-furo[2,3-d][1,3]dioxole
  参考文献：
  名称：

  Intramolecular [2 + 2] Photocycloaddition of Alkenes Incorporated in a Carbohydrate Template. Synthesis of Enantiopure Bicyclo[3.2.0]heptanes and -[6.3.0]undecanes

  摘要：

  Intramolecular [2 + 2] photocycloaddition of alkenes with a furano sugar placed between them have been investigated under both copper(l)-catalyzed and sensitized conditions. The copper(l)catalyzed photocycloaddition of the dienes 4a, 4b, and 4c led to unexpected formation of the thermodynamically less stable cis-syn-cis 4-5-5 tricyclic adducts 5a, 5b, and 5c, respectively. The sensitized photocycloaddition of the diene 14 also gave the cis-syn-cis adduct 15 showing that the copper(I) catalyst does not have any influence on the stereochemical course through coordination with the anomeric ring oxygen of the furano sugar. The identical stereochemical course observed under both catalyzed and sensitized photoaddition reactions have been attributed to be of steric origin. Bis(dienes) 25a and 25b, which gave an intractable mixture on copper(l)-catalyzed irradiation, underwent smooth photocycloaddition in the presence of benzophenone, and the resulting 1,2-divinyl cyclobutanes underwent spontaneous [3.3]-rearrangement at room temperature to produce bicyclo[6.3.0]undecanes 30a and 30b, respectively. This investigation provides an approach for the construction of enantiopure bicyclo[3.2.0]heptanes and -[6.3.0]undecanes.

  DOI：

  10.1021/jo026920c