(E)-3-methyl-4-(4-nitrophenyl)but-3-en-2-one | 26480-64-8

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: (E)-3-methyl-4-(4-nitrophenyl)but-3-en-2-one
• 英文别名: 4-(4-Nitrophenyl)-3-methyl-3-buten-2-one
• CAS: 26480-64-8
• 化学式: C₁₁H₁₁NO₃
• 分子量: 205.213
• InChiKey: HOSZCLQZBNGFIS-BQYQJAHWSA-N

物化性质

• 熔点：
  95-96 °C(Solv: benzene (71-43-2))
• 沸点：
  327.9±17.0 °C(Predicted)
• 密度：
  1.191±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-methyl-4-(4-nitrophenyl)but-3-en-2-one 在 ((4S)-2-(2-(diphenylphosphino)phenyl)-4-tert-butyl-4,5-dihydrooxazole)-(η4-1,5-cyclooctadiene)iridium(I) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate 、 氢气 作用下， 以 甲苯 为溶剂， 20.0 ℃ 、200.0 kPa 条件下， 反应 3.0h， 以88%的产率得到(S)-3-methyl-4-(4'-nitrophenyl)butan-2-one
  参考文献：
  名称：

  铱催化的不对称加氢反应对光学活性酮的高度对映选择性合成。

  摘要：

  DOI：

  10.1002/anie.200803709
• 作为产物：
  描述：

  (E)-3-methyl-4-phenyl-3-buten-2-one 在 硝酸 作用下， 生成 (E)-3-methyl-4-(4-nitrophenyl)but-3-en-2-one
  参考文献：
  名称：

  Mannich Bases from Benzalacetones

  摘要：

  DOI：

  10.1021/ja01154a107

文献信息

• Highly Enantioselective Iridium-Catalyzed Hydrogenation of Conjugated Trisubstituted Enones
  作者：Bram B. C. Peters、Jira Jongcharoenkamol、Suppachai Krajangsri、Pher G. Andersson

  DOI：10.1021/acs.orglett.0c04012

  日期：2021.1.1

  Asymmetric hydrogenation of conjugated enones is one of the most efficient and straightforward methods to prepare optically active ketones. In this study, chiral bidentate Ir–N,P complexes were utilized to access these scaffolds for ketones bearing the stereogenic center at both the α- and β-positions. Excellent enantiomeric excesses, of up to 99%, were obtained, accompanied with good to high isolated

  共轭烯酮的不对称氢化是制备光学活性酮的最有效，最直接的方法之一。在这项研究中，手性双齿Ir-N，P络合物被用于进入这些支架，以获得在α和β位置均具有立体中心的酮。获得了高达99％的出色的对映体过量，并具有良好或较高的分离产率。具有挑战性的二烷基取代的底物（很难通过令人满意的手性诱导进行氢化）以高度对映选择性的方式氢化。
• Stereodivergent Evolution of Artificial Enzymes for the Michael Reaction
  作者：Xavier Garrabou、Duncan Stuart Macdonald、Basile I. M. Wicky、Donald Hilvert

  DOI：10.1002/anie.201712554

  日期：2018.5.4

  Enzymes are valuable biocatalysts for asymmetric synthesis due to their exacting stereocontrol. Changing the selectivity of an existing catalyst for new applications is, however, challenging. Here we show that, in contrast, the stereoselectivity of an artificial enzyme created by design and directed evolution is readily tunable. We engineered a promiscuous artificial retro‐aldolase into four stereocomplementary

  酶由于严格的立体控制，是用于不对称合成的有价值的生物催化剂。然而，改变现有催化剂用于新用途的选择性是具有挑战性的。在这里，我们表明，相比之下，通过设计和定向进化产生的人工酶的立体选择性很容易调节。我们将混杂的人工逆醛缩酶设计成四种立体互补催化剂，用于将叔碳负离子迈克尔加成至不饱和酮上。值得注意的是，这种选择性也被其他迈克尔亲核试剂所保留。通过扩展这些方法，其他设计酶的完全立体多样化也应同样可能。
• The Knoevenagel Reactions of Aldehydes with Carboxy Compounds. I. Reactions of<i>p</i>-Nitrobenzaldehyde with Active Methine Compounds
  作者：Mayumi Tanaka、Osamu Oota、Hideo Hiramatsu、Kazuyoshi Fujiwara

  DOI：10.1246/bcsj.61.2473

  日期：1988.7

  The Knoevenagel reactions of p-nitrobenzaldehyde (1) with β-keto acids, methylmalonic (2a) and α-methylacetoacetic acids (2b) were carried out in the presence of a tertiary amine such as pyridine. We have isolated the corresponding β-hydroxy intermediate (3a) by the reaction of 2a which positively suggested the reaction proceeded by the Hann and Lapworth mechanism. A kinetic study using 1H NMR revealed the existence of the reversibility between the starting materials and the β-hydroxy intermediate and that the rate determining step was decarboxylattion. But, when using the secondary amine, both the β-hydroxy acid and the corresponding condensation product were obtained via this reaction. These findings led to the conclusion that the reaction proceeded according to the two competing mechanisms, i.e., the Hann and Lapworth and Knoevenagel mechanisms. It was further clarified that either the decarboxylation step or the formation of the bis(dialkylamino) derivative was the rate determining step. The stereoselectivity of the β-hydroxy saturated compound has been closely related to the fact that the conformation of the intermediate possesses an intramolecular hydrogen bond to a hydroxyl group.

  在三烷基胺如吡啶的存在下，进行对硝基苯甲醛（1）与β-酮酸、甲基丙二酸（2a）和α-甲基乙酰乙酸（2b）的Knoevenagel反应。通过2a的反应成功分离出相应的β-羟基中间体（3a），这一结果正面表明反应是通过Hann和Lapworth机制进行的。利用1H NMR的动力学研究表明，起始物质与β-羟基中间体之间存在可逆性，且决定反应速率的步骤是脱羧。然而，当使用二级胺时，通过此反应可同时得到β-羟基酸及其相应的缩合产物。这些发现导致结论，反应遵循两种竞争机制，即Hann和Lapworth机制与Knoevenagel机制。进一步明确，决定反应速率的步骤要么是脱羧步骤，要么是形成双(二烷基氨基)衍生物的步骤。β-羟基饱和化合物的立体选择性与中间体具有分子内氢键至羟基的构象密切相关。
• CuH-Catalyzed Enantioselective 1,2-Reductions of α,β-Unsaturated Ketones
  作者：Ralph Moser、Žarko V. Bošković、Christopher S. Crowe、Bruce H. Lipshutz

  DOI：10.1021/ja102689e

  日期：2010.6.16

  The first study on a general technology for arriving at valued nonracemic allylic alcohols using asymmetric ligand-accelerated catalysis by copper hydride is described.

  描述了使用氢化铜的不对称配体加速催化获得有价值的非外消旋烯丙醇的通用技术的第一项研究。
• Diels–Alder reaction of unsymmetrical dienes with unsymmetrical p-benzoquinones
  作者：M. F. Ansell、A. H. Clements

  DOI：10.1039/j39710000269

  日期：——

  A number of Diels–Alder reactions between 1-phenyl-, 1-p-methoxyphenyl-, and 1-p-nitrophenyl-2,3-dimethylbutadiene and methoxycarbonyl-, 2,6-dimethyl-, 2,5-dimethyl-, 2-methoxy-6-methyl-, 5-methoxy-2-methoxycarbonyl-3-methyl-, and 2-cyano-3,5-dimethyl-p-benzoquinone are reported. The structures of the major products are established and their formation is interpreted on the basis of a transition state

  1-苯基-，1-对甲氧基苯基-和1-对硝基苯基-2,3-二甲基丁二烯与甲氧基羰基-，2,6-二甲基-，2,5-二甲基-之间的许多Diels-Alder反应报道了2-甲氧基-6-甲基-，5-甲氧基-2-甲氧基羰基-3-甲基和2-氰基-3,5-二甲基-对苯醌。确定了主要产物的结构，并根据具有某些双自由基特征的过渡态解释了它们的形成。