(2R)-(E)-2,4-dimethyl-4-hexenal | 159254-36-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R)-(E)-2,4-dimethyl-4-hexenal
• 英文别名: (2R,4E)-2,4-dimethyl-hex-4-enal；(2R,4E)-2,4-dimethylhex-4-enal；(E,2R)-2,4-dimethylhex-4-enal
• CAS: 159254-36-1
• 化学式: C₈H₁₄O
• 分子量: 126.199
• InChiKey: QIGOHFLKAFHWDZ-RXLGXGPVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2R)-(E)-2,4-dimethyl-4-hexenal 在 cerium(III) chloride 、 potassium carbonate 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 methyl (E,2S,3S,4R)-3-hydroxy-2,4,6-trimethyloct-6-enoate
  参考文献：
  名称：

  Synthesis of the Aliphatic Depside (+)-Bourgeanic Acid

  摘要：

  The lichen metabolite (+)-bourgeanic acid (1) was synthesized in 12 steps and 3.4% overall yield from (R)-2-methyl-1-iodobutane (53) by a sequence which confirmed that this aliphatic depside is the self-esterification product of (2S,3S,4R,6R)-2,4,6-trimethyl-3-hydroxyoctanoic acid. Alkylation of the enolate of (S)-N-propionylprolinol (48) with 53 gave the amide 60 which was transformed to (2R,4R)-2,4-dimethylhexanal (4). The latter was reacted with the crotylboronate 68, prepared from (S,S)-(-)-diisopropyltartrate, to afford (3R,4S,5R,7R)-3,5,7-trimethyl-1-nonen-4-ol (65) as the major diastereomer. Protection followed by ozonolysis and oxidation furnished (-)-hemibourgeanic acid (2). The beta-lactone 73 derived from 2 was used to acylate 65, and the resulting ester 74 was subjected to oxidative ozonolysis to yield (+)-1.

  DOI：

  10.1021/jo00091a022
• 作为产物：
  描述：

  (2E)-1-溴-2-甲基-2-丁烯 在 lithium aluminium tetrahydride 、 草酰氯 、 二甲基亚砜 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 4.25h， 生成 (2R)-(E)-2,4-dimethyl-4-hexenal
  参考文献：
  名称：

  Synthesis of the Aliphatic Depside (+)-Bourgeanic Acid

  摘要：

  The lichen metabolite (+)-bourgeanic acid (1) was synthesized in 12 steps and 3.4% overall yield from (R)-2-methyl-1-iodobutane (53) by a sequence which confirmed that this aliphatic depside is the self-esterification product of (2S,3S,4R,6R)-2,4,6-trimethyl-3-hydroxyoctanoic acid. Alkylation of the enolate of (S)-N-propionylprolinol (48) with 53 gave the amide 60 which was transformed to (2R,4R)-2,4-dimethylhexanal (4). The latter was reacted with the crotylboronate 68, prepared from (S,S)-(-)-diisopropyltartrate, to afford (3R,4S,5R,7R)-3,5,7-trimethyl-1-nonen-4-ol (65) as the major diastereomer. Protection followed by ozonolysis and oxidation furnished (-)-hemibourgeanic acid (2). The beta-lactone 73 derived from 2 was used to acylate 65, and the resulting ester 74 was subjected to oxidative ozonolysis to yield (+)-1.

  DOI：

  10.1021/jo00091a022

文献信息

• Total Synthesis, Stereochemical Assignment, and Field-Testing of the Sex Pheromone of the Strepsipteran<i>Xenos peckii</i>
  作者：Huimin Zhai、Michael Hrabar、Regine Gries、Gerhard Gries、Robert Britton

  DOI：10.1002/chem.201505097

  日期：2016.4.25

  11‐tridecadienal. Herein we report the asymmetric synthesis of three candidate stereostructures for this pheromone using a synthetic strategy that relies on an sp3–sp2 Suzuki–Miyaura coupling to construct the correctly configured C7‐alkene function. Comparison of 1H NMR spectra derived from the candidate stereostructures to that of the natural sex pheromone indicated a relative configuration of (3R*,5S*,9R*). Chiral

  内寄生性昆虫Xenos peckii（Strepsiptera：Xenidae）的性信息素最近被鉴定为（7 E，11 E）-3,5,9,11-四甲基-7,11-十三碳二烯醛。在这里，我们报告了一种信息素的不对称合成，该信息素使用依赖于sp 3 –sp 2 Suzuki–Miyaura偶联的合成策略来构建正确配置的C7-烯烃功能的该信息素。从候选立体结构衍生的1 H NMR光谱与自然性信息素的1 H NMR光谱进行比较，发现相对构型为（3 R *，5 S *，9 R *）。这些化合物的手性气相色谱（GC）分析支持将天然产物指定为（3 R，5 S，9 R）。此外，在16个重复的野外实验中，单独或与（3 S，5 R，9 S）对映异构体组合使用合成（3 R，5 S，9 R）对映体诱捕的阱捕获了23和18 X 。peckii雄性，分别（平均值±SE：1.4±0.33和1.1±0.39），而诱捕器用合成诱饵诱捕（3
• Stereoselective synthesis of the C13–32 spiroacetal fragment of spirangien A
  作者：Claire Gregg、Michael V. Perkins

  DOI：10.1016/j.tet.2013.06.012

  日期：2013.8

  Stereoselective synthesis of an advanced intermediate towards the highly cytotoxic polyketide metabolite spirangien A was achieved. A key step in the synthesis was installation of the C23 stereocentre by a substrate controlled C22-23 aldol reaction. Comparison of this result with previous literature reports suggests that the facial preference of the aldehyde controls the outcome of the C22-23 aldol coupling and depends on the 027/25 protecting groups when reacting with complex ketones, which contain the C17-15 stereochemistry. (C) 2013 Elsevier Ltd. All rights reserved.
• Synthesis of the Aliphatic Depside (+)-Bourgeanic Acid
  作者：James D. White、Alan T. Johnson

  DOI：10.1021/jo00091a022

  日期：1994.6

  The lichen metabolite (+)-bourgeanic acid (1) was synthesized in 12 steps and 3.4% overall yield from (R)-2-methyl-1-iodobutane (53) by a sequence which confirmed that this aliphatic depside is the self-esterification product of (2S,3S,4R,6R)-2,4,6-trimethyl-3-hydroxyoctanoic acid. Alkylation of the enolate of (S)-N-propionylprolinol (48) with 53 gave the amide 60 which was transformed to (2R,4R)-2,4-dimethylhexanal (4). The latter was reacted with the crotylboronate 68, prepared from (S,S)-(-)-diisopropyltartrate, to afford (3R,4S,5R,7R)-3,5,7-trimethyl-1-nonen-4-ol (65) as the major diastereomer. Protection followed by ozonolysis and oxidation furnished (-)-hemibourgeanic acid (2). The beta-lactone 73 derived from 2 was used to acylate 65, and the resulting ester 74 was subjected to oxidative ozonolysis to yield (+)-1.