[tert-butyl(dimethyl)silyl] (E,3S)-3-methylhex-4-enoate | 1026655-31-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [tert-butyl(dimethyl)silyl] (E,3S)-3-methylhex-4-enoate
• CAS: 1026655-31-1
• 化学式: C₁₃H₂₆O₂Si
• 分子量: 242.434
• InChiKey: MZDDSGFWYNLASO-ANYFNZRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.14
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  [tert-butyl(dimethyl)silyl] (E,3S)-3-methylhex-4-enoate 在 盐酸 、 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 18.0h， 生成 (-)-(S,E)-3-Penten-2-yl (S,E)-3-methyl-4-hexenoate
  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,E)-3-Penten-2-yl acetate 、 叔丁基二甲基氯硅烷 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 生成 [tert-butyl(dimethyl)silyl] (E,3S)-3-methylhex-4-enoate
  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

文献信息

• Iterative enolate Claisen rearrangements: versatile route to optically pure 2,7-nonadiene-5-carboxylic acids
  作者：John C. McKew、Mark J. Kurth

  DOI：10.1021/jo00069a019

  日期：1993.8

  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.