8-oxo-8-phenyloct-6-enal | 190522-49-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 8-oxo-8-phenyloct-6-enal
• 英文别名: (E)-8-oxo-8-phenyloct-6-enal
• CAS: 190522-49-7
• 化学式: C₁₄H₁₆O₂
• 分子量: 216.28
• InChiKey: CYANNSZLLVWFKH-YRNVUSSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  8-oxo-8-phenyloct-6-enal 在 (4R)-N-(naphthyl)-2,2-Me₂-thiazolidine-4-carboxamide trifluoroacetate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 4.17h， 生成 (1R,2S)-2-(2-oxo-2-phenylethyl)-cyclopentanecarbaldehyde
  参考文献：
  名称：

  Cysteine-Derived Organocatalyst in a Highly Enantioselective Intramolecular Michael Reaction

  摘要：

  Asymmetric intramolecular Michael reaction catalyzed by an organocatalyst derived from cysteine has been developed for the synthesis of chiral bicyclo[4.3.0]nonene and cis-disubstituted cyclopentane skeletons with a creation of three or two contiguous chiral centers in good yield with high diastereo- and excellent enantioselectivities.

  DOI：

  10.1021/ja055740s
• 作为产物：
  描述：

  1,6-己二醇 在 碳酸氢钠 吡啶 、 4-二甲氨基吡啶 、 2,2,6,6-tetramethyl-piperidine-N-oxyl 、 sodium hypochlorite 、 乙酸酐 、 对甲苯磺酸 、 potassium bromide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 75.0h， 生成 8-oxo-8-phenyloct-6-enal
  参考文献：
  名称：

  Cysteine-Derived Organocatalyst in a Highly Enantioselective Intramolecular Michael Reaction

  摘要：

  Asymmetric intramolecular Michael reaction catalyzed by an organocatalyst derived from cysteine has been developed for the synthesis of chiral bicyclo[4.3.0]nonene and cis-disubstituted cyclopentane skeletons with a creation of three or two contiguous chiral centers in good yield with high diastereo- and excellent enantioselectivities.

  DOI：

  10.1021/ja055740s

文献信息

• Asymmetric Intramolecular Michael Reaction Catalyzed by Proline-Derived Small Anilides
  作者：Hisao Nishiyama、Makoto Kikuchi、Tomohiko Inagaki

  DOI：10.1055/s-2007-977421

  日期：2007.4

  Simple proline-derived anilide-catalyzed asymmetric -intramolecular Michael reaction was described. Chiral cyclic keto-aldehydes were obtained from acyclic formyl enones in excellent yields with good stereoselectivity. The reaction proceeded in exceptionally fast with a commercially available proline anilide. On the other hand, the longer reaction time conduced toward the higher -diastereoselectivity

  描述了简单的脯氨酸衍生的苯胺催化的不对称分子内迈克尔反应。手性环状酮醛是从无环甲酰基烯酮以优异的收率和良好的立体选择性获得的。使用市售的脯氨酸苯胺，反应进行得异常快。另一方面，通过环状酮醛的有利异构化，较长的反应时间有助于更高的非对映选择性。
• Assessing the scope of the tandem Michael/intramolecular aldol reaction mediated by secondary amines, thiols and phosphines
  作者：Elinor L Richards、Patrick J Murphy、Francesca Dinon、Silvia Fratucello、Paul M Brown、Thomas Gelbrich、Michael B Hursthouse

  DOI：10.1016/s0040-4020(01)00744-x

  日期：2001.9

  The outcome of a tandem Michael/intramolecular aldol reaction which is mediated by secondary amines, thiols and phosphines has been found to be highly substrate dependent, with the best results being obtained for the formation of 5 and 6-membered rings using thiol or thiolate nucleophiles. Amine and phosphine mediated cyclisations were found to be problematic in several cases but were still effective

  已发现由仲胺，硫醇和膦介导的串联迈克尔/分子内羟醛反应的结果高度依赖于底物，使用硫醇或硫醇盐亲核试剂形成5元和6元环可获得最佳结果。发现胺和膦介导的环化在某些情况下是有问题的，但仍然是形成5-7元环的有效方法。
• Nickel-Catalyzed Organozinc-Promoted Carbocyclizations of Electron-Deficient Alkenes with Tethered Unsaturation
  作者：John Montgomery、Eric Oblinger、Alexey V. Savchenko

  DOI：10.1021/ja9702125

  日期：1997.5.1

  A nickel-catalyzed method for cyclizations of electron-deficient alkenes with tethered unsaturation in the presence of organozincs was developed. Considerable flexibility in the structure of each reactive component was observed. Enones, alkylidene malonates, unsaturated β-ketoesters, and nitroalkenes participated as the electron-deficient alkene; alkynes, enones, 1,3-dienes, and aldehydes participated

  开发了一种镍催化的方法，用于在有机锌存在下对具有束缚不饱和度的缺电子烯烃进行环化。观察到每个反应组件的结构具有相当大的灵活性。烯酮、亚烷基丙二酸酯、不饱和β-酮酯和硝基烯烃作为缺电子烯烃参与；炔烃、烯酮、1,3-二烯和醛作为系链不饱和键参与；以及各种 sp2 和 sp3 杂化的有机锌，包括那些具有 β-氢的有机锌，作为亲核组分参与其中。底物结构、有机锌结构和配体结构都在决定产物选择性方面发挥了重要作用。具有特殊合成意义的是从普通炔烃制备 E 或 Z 三或四取代烯烃的机会。
• Antibody-Catalyzed Asymmetric Intramolecular Michael Addition of Aldehydes and Ketones to Yield the Disfavored Cis-Product
  作者：Roy Weinstain、Richard A. Lerner、Carlos F. Barbas、Doron Shabat

  DOI：10.1021/ja0536825

  日期：2005.9.28

  The development of new catalytic asymmetric reactions continues to be a major goal in organic chemistry. Here we report a novel antibody-catalyzed intramolecular Michael addition of aldehydes and ketones to enones. The reaction is enantioselective and diastereoselective with a high ee value and cis/trans ratio. This is the first example of asymmetric intramolecular Michael addition of ketones. Antibody

  开发新的催化不对称反应仍然是有机化学的主要目标。在这里，我们报告了一种新型抗体催化的醛和酮与烯酮的分子内迈克尔加成。该反应具有对映选择性和非对映选择性，具有高 ee 值和顺/反比。这是酮的不对称分子内迈克尔加成的第一个例子。抗体 38C2 是迄今为止唯一能够在迈克尔加成产物中产生这种选择性的催化剂。
• Role of Hydrogen-Bonding Acceptors in Organo-Enamine Catalysis
  作者：Junbin Han、Zhichao Lu、Andrew L. Flach、Robert S. Paton、Gerald B. Hammond、Bo Xu

  DOI：10.1002/chem.201502407

  日期：2015.8.10

  A hydrogen bond acceptor plays an important role in the catalytic cycle of organo‐enamine catalysis. It can effectively influence the rate of reaction through hydrogen bonding interaction with enammonium (N‐protonated enamine intermediate). Our findings are supported by both kinetic experiments and quantum chemical calculations.

  氢键受体在有机烯胺催化的催化循环中起着重要作用。它可以通过氢与am（N质子化的烯胺中间体）发生氢键相互作用来有效地影响反应速率。我们的发现得到动力学实验和量子化学计算的支持。