methyl 2-(3-chlorophenyl)-2-oxoacetate | 34966-50-2

• 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: methyl 2-(3-chlorophenyl)-2-oxoacetate
• CAS: 34966-50-2
• 化学式: C₉H₇ClO₃
• 分子量: 198.606
• InChiKey: LLOQGKAPBBNIPV-UHFFFAOYSA-N

物化性质

• 熔点：
  44-45 °C
• 沸点：
  292.2±23.0 °C(Predicted)
• 密度：
  1.298±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.11
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-(3-chlorophenyl)-2-oxoacetate 在 甲醇 、 苯甲醛 、 1,3-双(2,4,6-三甲基苯基)氯化咪唑 、 三乙胺 作用下， 反应 5.0h， 以95%的产率得到methyl 2-(3-chlorophenyl)-2-hydroxyacetate
  参考文献：
  名称：

  1,3-Bis(2,4,6-trimethylphenyl)imidazolium chloride in combination with triethylamine: an improved catalytic system for hydroacylation/reduction of activated ketones

  摘要：

  A rapid, economic, and high yielding methodology has been developed for hydroacylation/reduction of activated ketones by using 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride as a catalyst in combination with triethylamine. The reaction proceeded at an ambient temperature via generating N-heterocyclic carbene in situ that interacted with the (hetero)aryl aldehyde employed. While the reduction of ketones takes place in MeOH, the hydroacylation process was found to be effective in THF for both electron rich and deficient aldehydes. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2010.12.022
• 作为产物：
  描述：

  methyl 2-(3-chlorophenyl)-2-hydroxyacetate 在 sodium bromide 作用下， 以 二氯甲烷 、 水 为溶剂， 以92%的产率得到methyl 2-(3-chlorophenyl)-2-oxoacetate
  参考文献：
  名称：

  Facile Synthesis of α- Keto Carbonyl Compounds by Indirect Anodic Oxidation

  摘要：

  邻位碳原子上具有羰基的二级醇在电化学氧化条件下顺利转化为相应的α-酮羰基化合物，产率良好。因此，芳香族α-羟基酯在未分隔的电池中可以轻松转化为芳基乙二酸酯，产率极高，而α-羟基酮和脂肪族α-羟基酯在分隔的电池中经过高效的阳极氧化也成功转化为相应的α-酮羰基化合物。

  DOI：

  10.1246/cl.1994.1017

文献信息

• Iridium-Catalyzed Asymmetric Hydrogenation of Unsaturated Piperazin-2-ones
  作者：Yanzhao Wang、Yuanyuan Liu、Kun Li、Guoqiang Yang、Wanbin Zhang

  DOI：10.1002/adsc.201700175

  日期：2017.6.6

  ruthenocene-based phosphine-oxazoline ligand tBu-mono-RuPHOX or the diphosphine ligand BINAP, were developed for the asymmetric hydrogenation of 5,6-dihydropyrazin-2(1H)-ones, affording chiral piperazin-2-ones in good yields and with moderate to good ees. Different catalytic behaviors for the hydrogenation of these types of substrate were observed with these two catalyst systems. Our tBu-mono-RuPHOX ligand, which

  从基于钌茂茂的膦-恶唑啉配体t Bu-mono-RuPHOX或二膦配体BINAP生成的两种不同的铱催化剂体系用于5,6-二氢吡嗪-2（1 H）-的不对称氢化，得到手性哌嗪-2-酮，收率高，ee中等至良好。用这两种催化剂体系观察到用于这些类型的底物氢化的不同催化行为。我们的t Bu-mono-RuPHOX配体带有带有手性的钌茂茂骨架，被发现是[Ir（L）（COD）] BArF催化剂体系的最佳配体，可提供所需的产物，ee最高可达94％。
• Direct asymmetric hydrogenation of α-keto acids by using the highly efficient chiral spiro iridium catalysts
  作者：Pu-Cha Yan、Jian-Hua Xie、Xiang-Dong Zhang、Kang Chen、Yuan-Qiang Li、Qi-Lin Zhou、Da-Qing Che

  DOI：10.1039/c4cc07643e

  日期：——

  A new efficient and highly enantioselective direct asymmetric hydrogenation of alpha-keto acids employing the Ir/SpiroPAP catalyst under mild reaction conditions has been developed. This method might be feasible for the preparation of a series of chiral alpha-hydroxy acids on a large scale.

  已经开发了在温和的反应条件下使用Ir / SpiroPAP催化剂的新型高效且高对映选择性的α-酮酸直接不对称氢化反应。该方法对于大规模制备一系列手性α-羟基酸可能是可行的。
• Visible Light Promotes Decyanation Esterification Reaction of β-Ketonitriles with Dioxygen and Alcohols to α-Ketoesters
  作者：Cheng Guo、Chen Xu、Nan-Nan Zhang、Xiao-ji Li、Yan-qin Ge、Pin-hui Diao

  DOI：10.1055/s-0036-1591943

  日期：2018.5

  A green and mild method has been developed for the conversion of β-ketonitriles into α-ketoesters under catalyst-free conditions. A plausible mechanism is that visible light promotes singlet oxygen generation to form the products through oxidative C–H bond functionalization and C–C σ -bond cleavage.

  开发了一种绿色温和的方法，用于在无催化剂条件下将 β-酮腈转化为 α-酮酯。一个合理的机制是可见光通过氧化 C-H 键功能化和 C-C σ 键裂解促进单线态氧的产生以形成产物。
• Chiral <i>N</i>,<i>N′</i>-Dioxide/Lanthanide(III) Complex Catalyzed Asymmetric Bisvinylogous Mukaiyama Aldol Reactions
  作者：Kai Fu、Jingchuan Zhang、Lili Lin、Jun Li、Xiaohua Liu、Xiaoming Feng

  DOI：10.1021/acs.orglett.6b03470

  日期：2017.1.20

  complexes have been developed as efficient catalysts for the bisvinylogous Mukaiyama aldol reaction of silyl ketene acetal with α-ketoesters and aldehydes, respectively. The catalytic systems were highly ε-selective, and the substrate scope was wide. The corresponding ε-hydroxy-α,β,γ,δ-unsaturated esters were obtained in up to 95% yield and 98% ee.

  已开发出手性N，N'-二氧化物/ Y（OTf）3和Sc（OTf）3配合物，分别作为甲硅烷基乙烯酮缩醛与α-酮酸酯和醛类双乙烯基木的Mukaiyama aldol反应的有效催化剂。催化体系具有高度的ε选择性，并且底物范围广。以高达95％的收率和98％的ee获得相应的ε-羟基-α，β，γ，δ-不饱和酯。
• Access to Chiral Tertiary α-Hydroxy-β-Ynyl Esters via One-Pot Addition and Kinetic Resolution
  作者：Hong-Bin Chen、Wen-Han Lai、Yan Zhao、Dan-Dan Qin、Yuan-Ping Ruan、Zhao-Hui Zhou

  DOI：10.1055/s-0033-1340824

  日期：——

  Chiral amino alcohol promoted one-pot addition of zinc alkynylides to α-keto esters and kinetic resolution of the resulting tertiary propargylic alcohols was developed. The reaction provided us an alternative approach to access optically active tertiary α-hydroxy-β-ynyl esters with enantiomeric excesses up to 98%.

  手性氨基醇促进了炔酸锌向 α-酮酯的一锅加成，并开发了所得叔炔丙醇的动力学拆分。该反应为我们提供了一种替代方法来获得对映体过量高达 98% 的光学活性叔 α-羟基-β-炔基酯。