(-)-(S,S,E,E)-4,6-Dimethyl-5-(hydroxymethyl)nona-2,7-diene | 150661-65-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (-)-(S,S,E,E)-4,6-Dimethyl-5-(hydroxymethyl)nona-2,7-diene
• 英文别名: (E,3S)-3-methyl-2-[(E,2S)-pent-3-en-2-yl]hex-4-en-1-ol
• CAS: 150661-65-7
• 化学式: C₁₂H₂₂O
• 分子量: 182.306
• InChiKey: KTKXEYKUTZCBKP-KXPLMPRYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-(+)-α-甲氧基-α-(三氟甲基)苯乙酸 、 (-)-(S,S,E,E)-4,6-Dimethyl-5-(hydroxymethyl)nona-2,7-diene 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 5.0h， 生成 (R,E)-2-<(R,E)-1-Methyl-2-butenyl>-3-methyl-4-hexen-1-yl (R)-α-methoxy-α-(trifluoromethyl)phenylacetate 、 (S,E)-2-<(S,E)-1-Methyl-2-butenyl>-3-methyl-4-hexen-1-yl (R)-α-methoxy-α-(trifluoromethyl)phenylacetate 、 (2R*,3S*,E)-2-<(R*,E)-1-Methyl-2-butenyl>-3-methyl-4-hexen-1-yl (R)-α-methoxy-α-(trifluoromethyl)phenylacetate
  参考文献：
  名称：

  Iterative enolate Claisen rearrangements: versatile route to optically pure 2,7-nonadiene-5-carboxylic acids

  摘要：

  A short, versatile, and diastereoselective method of preparing 2,7-nonadiene-5-carboxylic acids by an iterative enolate Claisen rearrangement procedure has been developed. Homochiral (E)- and (Z) secondary allylic alcohols 1-4, prepared from (S)-(-)-ethyl lactate, were esterified with acetic acid and enolized, and the resulting silyl ketene acetals were warmed to room temperature to effect [3,3]-sigmatropic rearrangement to 4-hexenoic acids 5-8. Esterification of these acids with alcohols 1-4 followed by a second enolate Claisen rearrangement delivered the targeted 2,7-nonadiene-5-carboxylic acids with high diastereoselectivity. This second [3,3]-sigmatropic rearrangement provides well-placed and potentially synthetically useful functionality and stereochemistry.

  DOI：

  10.1021/jo00069a019
• 作为产物：
  描述：

  (-)-(S,S,E,E)-4,6-Dimethylnona-2,7-diene-5-carboxylic acid 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.0h， 以84%的产率得到(-)-(S,S,E,E)-4,6-Dimethyl-5-(hydroxymethyl)nona-2,7-diene
  参考文献：
  名称：

  Iterative enolate Claisen rearrangements: versatile route to optically pure 2,7-nonadiene-5-carboxylic acids

  摘要：

  A short, versatile, and diastereoselective method of preparing 2,7-nonadiene-5-carboxylic acids by an iterative enolate Claisen rearrangement procedure has been developed. Homochiral (E)- and (Z) secondary allylic alcohols 1-4, prepared from (S)-(-)-ethyl lactate, were esterified with acetic acid and enolized, and the resulting silyl ketene acetals were warmed to room temperature to effect [3,3]-sigmatropic rearrangement to 4-hexenoic acids 5-8. Esterification of these acids with alcohols 1-4 followed by a second enolate Claisen rearrangement delivered the targeted 2,7-nonadiene-5-carboxylic acids with high diastereoselectivity. This second [3,3]-sigmatropic rearrangement provides well-placed and potentially synthetically useful functionality and stereochemistry.

  DOI：

  10.1021/jo00069a019