(-)-(E,3R)-3-ethyl-4-hexenoic acid | 116195-27-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (-)-(E,3R)-3-ethyl-4-hexenoic acid
• 英文别名: (-)-(R,E)-3-Ethyl-4-hexenoic acid；(E,3R)-3-ethylhex-4-enoic acid
• CAS: 116195-27-8
• 化学式: C₈H₁₄O₂
• 分子量: 142.198
• InChiKey: QTUNTBHTJDVKBJ-MZTFZBDOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (-)-(E,3R)-3-ethyl-4-hexenoic acid 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 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 17.0h， 生成 (R,E)-3-Ethyl-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：

  (Z)-(S)-Hex-3-en-2-ol 在 盐酸 、 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 50.08h， 生成 (-)-(E,3R)-3-ethyl-4-hexenoic acid
  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

• Asymmetric Induction at C(?) and C(?) ofN-Enoylsultams by Organomagnesium 1,4-Addition/Enolate Trapping
  作者：Wolfgang Oppolzer、Giovanni Poli、Arend J. Kingma、Christian Starkemann、G�rald Bernardinelli

  DOI：10.1002/hlca.19870700825

  日期：1987.12.16

  The 1,4-addition of alkylmagnesium chlorides to conjugated N-enoylsultams and subsequent ‘enolate trapping’ with aq. NH4Cl or MeI/hexamethylphosphoric triamide generated centers of asymmetry at C(β) and/or at C(α) with good to excellent π-face defferentiation as demonstrated by the conversions 12, 14, and 89. This holds also for the regioselective 1,4-addition of EtMgC1 to a dienoylsultam (1516). Reactive

  烷基镁氯化物在1,4-加成反应中与共轭N-烯酰基阿磺酰胺结合，随后用碳酸氢钠水溶液进行“烯醇式捕集”。NH 4 Cl或将MeI /六甲基磷酰胺中C（β）和/或在C（α）具有良好的作为表明由转化优良π共面defferentiation产生不对称中心1 2，1 4，和8 9。这也适用于将EtMgC1在区域选择性地1，4-加成至二烯丙基舒马坦（15 16）。反应构象1 ≠，8 ≠，13和14假定X射线证据与X射线证据一致，X射线证据也用于确定产物9j的结构。
• OPPOLZER, WOLFGANG;POLI, GIOVANNI;KINGMA, AREND J.;STARKEMANN, CHRISTIAN;+, HELV. CHIM. ACTA, 70,(1987) N 8, 2201-2214
  作者：OPPOLZER, WOLFGANG、POLI, GIOVANNI、KINGMA, AREND J.、STARKEMANN, CHRISTIAN、+

  DOI：——

  日期：——
• 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.