5-acetoxy-3,3-diisopropenylvaleraldehyde | 315195-09-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 5-acetoxy-3,3-diisopropenylvaleraldehyde
• 英文别名: [4-Methyl-3-(2-oxoethyl)-3-prop-1-en-2-ylpent-4-enyl] acetate
• CAS: 315195-09-6
• 化学式: C₁₃H₂₀O₃
• 分子量: 224.3
• InChiKey: YEYCSPNSFRLLBO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-acetoxy-3,3-diisopropenylvaleraldehyde 在 [Rh(R)-BINAP]ClO₄ 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以88%的产率得到(3S,4S)-3-(2-acetoxyethyl)-3-isopropenyl-4-methylcyclopentanone
  参考文献：
  名称：

  Enantio- and diastereoselective construction of 4,9-dimethylspiro[4.4]nonane-2,7-dione using Rh-catalyzed asymmetric cyclization

  摘要：

  Asymmetric cyclization using Rh-complexes was applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing a chiral quaternary carbon could be stepwisely constructed by using Rh-catalyzed cyclization twice. All diastereomers of the spirodiketone could be stereoselectively prepared from the identical starting material by the combination of a neutral Rh(PPh3)(3)Cl and a cationic Rh[BINAP]ClO4. The cyclization by the neutral Rh(PPh3)(3)Cl proceeded to give cis-3,4-disubstituted cyclopentanones, while that by the cationic Rh[BINAP]ClO4 proceeded to afford trans-3,4-disubstituted cyclopentanones. Four spirodiketones of six stereoisomers could be prepared in optically active form, and the relationship between the stereochemistry of the spirodiketones and the Rh-complex was discussed based on the plausible acyl-hydride Rh-complexes. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)01106-6
• 作为产物：
  描述：

  3,3-二乙酰基丙酸甲酯 在 吡啶 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 potassium tert-butylate 、 sodium acetate 、 四氯化钛 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 27.25h， 生成 5-acetoxy-3,3-diisopropenylvaleraldehyde
  参考文献：
  名称：

  Enantio- and diastereoselective construction of 4,9-dimethylspiro[4.4]nonane-2,7-dione using Rh-catalyzed asymmetric cyclization

  摘要：

  Asymmetric cyclization using Rh-complexes was applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing a chiral quaternary carbon could be stepwisely constructed by using Rh-catalyzed cyclization twice. All diastereomers of the spirodiketone could be stereoselectively prepared from the identical starting material by the combination of a neutral Rh(PPh3)(3)Cl and a cationic Rh[BINAP]ClO4. The cyclization by the neutral Rh(PPh3)(3)Cl proceeded to give cis-3,4-disubstituted cyclopentanones, while that by the cationic Rh[BINAP]ClO4 proceeded to afford trans-3,4-disubstituted cyclopentanones. Four spirodiketones of six stereoisomers could be prepared in optically active form, and the relationship between the stereochemistry of the spirodiketones and the Rh-complex was discussed based on the plausible acyl-hydride Rh-complexes. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)01106-6

文献信息

• Application of Rh-catalyzed cyclization for the construction of three consecutive chiral carbons in 4,9-dimethylspiro[4.4]nonane-2,7-dione
  作者：Miyuki Takahashi、Masakazu Tanaka*、Eishi Sakamoto、Masanori Imai、Akiko Matsui、Kazuhisa Funakoshi、Kiyoshi Sakai、Hiroshi Suemune

  DOI：10.1016/s0040-4039(00)01315-0

  日期：2000.10

  Asymmetric cyclization using Rh-complexes has been applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing three consecutive chiral carbons could be stepwisely constructed from an identical starting material by the combination of a cationic Rh[(S)BINAP]ClO4 and a neutral RhCl(PPh3)(3). The relationship between the stereochemistry of the spirodiketones and the Rh-complex was also discussed. (C) 2000 Elsevier Science Ltd. All rights reserved.
• Enantio- and diastereoselective construction of 4,9-dimethylspiro[4.4]nonane-2,7-dione using Rh-catalyzed asymmetric cyclization
  作者：Masakazu Tanaka、Miyuki Takahashi、Eishi Sakamoto、Masanori Imai、Akiko Matsui、Masakazu Fujio、Kazuhisa Funakoshi、Kiyoshi Sakai、Hiroshi Suemune

  DOI：10.1016/s0040-4020(00)01106-6

  日期：2001.2

  Asymmetric cyclization using Rh-complexes was applied to the synthesis of 4,9-dimethylspiro[4.4]nonane-2,7-diones. The spiro[4.4]nonane skeleton bearing a chiral quaternary carbon could be stepwisely constructed by using Rh-catalyzed cyclization twice. All diastereomers of the spirodiketone could be stereoselectively prepared from the identical starting material by the combination of a neutral Rh(PPh3)(3)Cl and a cationic Rh[BINAP]ClO4. The cyclization by the neutral Rh(PPh3)(3)Cl proceeded to give cis-3,4-disubstituted cyclopentanones, while that by the cationic Rh[BINAP]ClO4 proceeded to afford trans-3,4-disubstituted cyclopentanones. Four spirodiketones of six stereoisomers could be prepared in optically active form, and the relationship between the stereochemistry of the spirodiketones and the Rh-complex was discussed based on the plausible acyl-hydride Rh-complexes. (C) 2001 Elsevier Science Ltd. All rights reserved.