(3aR,5S,6R,6aR)-6-Benzyloxy-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde | 541508-12-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (3aR,5S,6R,6aR)-6-Benzyloxy-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde
• CAS: 541508-12-7
• 化学式: C₂₁H₂₆O₅
• 分子量: 358.434
• InChiKey: FWRJCUYFWABVAF-RCLSDMTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.54
• 重原子数：
  26.0
• 可旋转键数：
  7.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  烯丙基三苯基氯化膦 、 (3aR,5S,6R,6aR)-6-Benzyloxy-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde 在 正丁基锂 作用下， 以 乙醚 、 正己烷 为溶剂， 以61%的产率得到(3aR,5R,6R,6aR)-6-Benzyloxy-5-((E)-buta-1,3-dienyl)-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-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
• 作为产物：
  描述：

  1-[(3aR,5R,6R,6aR)-6-Benzyloxy-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-tetrahydro-furo[2,3-d][1,3]dioxol-5-yl]-ethane-1,2-diol 在 sodium periodate 作用下， 以 水 、 乙腈 为溶剂， 反应 1.0h， 以720 mg的产率得到(3aR,5S,6R,6aR)-6-Benzyloxy-2,2-dimethyl-6-((E)-4-methyl-penta-2,4-dienyl)-tetrahydro-furo[2,3-d][1,3]dioxole-5-carbaldehyde
  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