4-cyclohexylbuta-2,3-dienoic acid | 257862-03-6

• 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: 4-cyclohexylbuta-2,3-dienoic acid
• CAS: 257862-03-6
• 化学式: C₁₀H₁₄O₂
• 分子量: 166.22
• InChiKey: GBNJYPUBSLCWIL-UHFFFAOYSA-N

物化性质

• 沸点：
  312.2±9.0 °C(Predicted)
• 密度：
  1.092±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.36
• 重原子数：
  12.0
• 可旋转键数：
  2.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  4-cyclohexylbuta-2,3-dienoic acid 在 四(三苯基膦)钯 、 氯化亚砜 、 potassium carbonate 、 三乙胺 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 生成 1-benzyl-5-c-hexyl-5-hydroxy-4-phenylpyrrol-2(5H)-one
  参考文献：
  名称：

  Steric Hindrance-Controlled Pd(0)-Catalyzed Coupling−Cyclization of 2,3-Allenamides and Organic Iodides. An Efficient Synthesis of Iminolactones and γ-Hydroxy-γ-lactams

  摘要：

  Under the catalysis of 1 mol % Pd(PPh3)(4), the reaction of 4,4-disubstituted 2,3-allenamides and organic iodides in toluene afforded iminolactones stereospecifically in >90% yields using K2CO3 (2 equiv)-5 mol % TBAB as the base. A similar reaction with 4-monosubstituted 2,3-allenamides afforded gamma-hydroxy-gamma-lactams in relatively lower yields. The N/O-attack selectivity may be determined by the steric effect at the 4-position of 2,3-allenamides.

  DOI：

  10.1021/jo025967v
• 作为产物：
  描述：

  二氧化碳 、 环己基丙二醇 在 正丁基锂 作用下， 生成 4-cyclohexylbuta-2,3-dienoic acid
  参考文献：
  名称：

  CuX₂-Mediated Cyclization Reaction of 2,3-Allenoic Acids. An Efficient Route to β-Halobutenolides

  摘要：

  DOI：

  10.1021/jo991574t

文献信息

• Reaction of PhSeCl or PhSCl with 2,3-Allenoic Acids: An Efficient Synthesis of β-Organoselenium or β-Organosulfur Substituted Butenolides
  作者：Shengming Ma、Feng Pan、Xueshi Hao、Xian Huang

  DOI：10.1055/s-2003-43377

  日期：——

  β-Organoselenium or β-organosulfur-substituted butenolides were prepared via the electrophilic cyclization of 2,3-allenoic acids with PhSeCl or PhSCl.

  δ-有机硒或δ-有机硫取代的丁烯内酯是通过 2,3-allenoic acids 与 PhSeCl 或 PhSCl 的亲电环化反应制备的。
• One-Step Asymmetric Construction of 1,4-Stereocenters via Tandem Mannich-Isomerization Reactions Mediated by a Dual-Functional Betaine Catalyst
  作者：Yu Deng、Xiaohuo Shi、Guangfa Shi、Xingyu Lu、Jisheng Luo、Li Deng

  DOI：10.1021/jacsau.2c00465

  日期：2022.12.26

  Mannich-isomerization reaction that allows the direct construction of 1,4-stereocenters in a highly stereoselective manner. This asymmetric transformation demonstrated the potential of a tandem nucleophilic addition-isomerization reaction as a broadly useful strategy for the efficient construction of 1,4-stereocenters. Notably, this tandem reaction was mediated by a single chiral betaine as a dual-functional

  包含不相邻立体中心的手性基序的构建是一项重大挑战，因为它们通常是使用不同的手性催化剂在不同的步骤中构建的。因此，开发简化此类复杂基序构造的新策略已成为不对称合成的主要焦点。我们在此报告了前所未有的不对称串联曼尼希异构化反应，该反应允许以高度立体选择性的方式直接构建 1,4-立体中心。这种不对称转化证明了串联亲核加成异构化反应作为有效构建 1,4-立体中心的广泛有用策略的潜力。值得注意的是，这种串联反应是由作为双功能催化剂的单一手性甜菜碱介导的，
• Enantioselective synthesis of β-arylbutenolides via palladium(0) catalysed asymmetric coupling cyclisation reaction of racemic allenic carboxylic acids with aryl iodides
  作者：Shengming Ma、Zhangjie Shi、Shulin Wu

  DOI：10.1016/s0957-4166(01)00046-5

  日期：2001.2

  Bis(oxazoline) 2c was used as a chiral ligand in the Pd(0) catalysed enantioselective coupling cyclisation of 2.3-allenoic acids with aryl iodides affording butenolides: in reasonable fields and with e.e.s of up to 53%. (C) 2001 Elsevier Science Ltd. All rights reserved.
• <i>trans</i>-RhCl(CO)(PPh₃)₂-Catalyzed Monomeric and Dimeric Cycloisomerization of Propargylic 2,3-Dienoates. Establishment of α,β-Unsaturated δ-Lactone Rings by Cyclometallation
  作者：Xuefeng Jiang、Shengming Ma

  DOI：10.1021/ja073582u

  日期：2007.9.1

  Cyclometallation of two unsaturated carbon-carbon bonds usually requires the application of low-valent metal catalysts, which could cleave the propargylic ester linkage. Thus, it is desirable to identify a catalyst which could undergo cyclometallation without cleaving the propargylic ester linkage. In this paper, we used trans-RhCI(CO)(PPh3)(2) to realize the cyclometallation of propargylic 2,3-dienoates. The substituents at the 4-position of allenoate moiety nicely control the reaction pathway: when the 4-position of propargylic 2,3-dienoate 1 was monosubstituted with an aryl group, the bicyclic intermediate 7 formed by the cyclometallation could highly selectively undergo carbometalation with the alkyne moiety in the second molecule of propargylic 2,3-dienoate 1 to afford metallabicyclic intermediates 8a or 8b. Subsequent reductive elimination would afford 9, which could undergo an intramolecular Diels-Alder reaction resulting in the formation of polycyclic bis(delta-lactone)-containing structures 2. The intermediate could be trapped by adding 3-methoxyprop-1-yne affording cyclization-aromatization product 4p highly selectively. If the substituent at the 4-positon of the 2,3-allenoate moiety has a beta-H atom, sequential unimolecular cyclometallation/beta-H elimination/reductive elimination occurs to afford cross-conjugated 5(Z)-alkylidene-4-alkenyl-5,6-dihydropyran-2-ones. The Z-stereochemistry of the exo double bond was determined by the cyclometallation. Some of the a,p-unsaturated delta-lactones could be easily converted to other synthetically useful compounds via reduction reaction, hydrogenation, and iodination/coupling protocol.
• HAHN, G.;ZWEIFEL, G., SYNTHESIS, BRD, 1983, N 11, 883-885
  作者：HAHN, G.、ZWEIFEL, G.

  DOI：——

  日期：——