methyl 2-(4-methylbenzyl)-3-oxo-butanoate | 1203476-25-8

• 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-(4-methylbenzyl)-3-oxo-butanoate
• 英文别名: Methyl 2-[(4-methylphenyl)methyl]-3-oxobutanoate；methyl 2-[(4-methylphenyl)methyl]-3-oxobutanoate
• CAS: 1203476-25-8
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: DLCNYNHUVXZIQT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 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-(4-methylbenzyl)-3-oxo-butanoate 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 24.0h， 生成 methyl α-(4-methylbenzyl)diazoacetate
  参考文献：
  名称：

  重氮酯催化不对称插入芳基-CHO 键：手性全碳四元中心的高度对映选择性构建

  摘要：

  本文描述了一种催化对映选择性路线，通过硼路易斯酸促进的重氮酯形式的 CC 插入芳基-CHO 键来合成功能化的全碳季无环系统。在手性 (S)-oxazaborolidinium 阳离子 1d 作为催化剂存在下，反应以良好的收率（高达 83%）、良好的区域选择性（高达 88:12）和优异的对映选择性（高达 99% ee）进行。该方法的合成潜力通过将产物转化为 α- 和 β- 氨基酯来说明。

  DOI：

  10.1021/ja408196g
• 作为产物：
  描述：

  methyl 2-(4-methylbenzylidene)-3-oxobutanoate 在 三乙基硅烷 、 iron(III) chloride hexahydrate 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 以92%的产率得到methyl 2-(4-methylbenzyl)-3-oxo-butanoate
  参考文献：
  名称：

  FeCl 3 ·6H 2 O催化亚烷基-β-酮酯和亚烷基-1,3-二酮的选择性共轭还原

  摘要：

  成功开发了FeCl 3 ·6H 2 O /三乙基硅烷复合催化剂体系，用于在温和的反应条件下选择性共轭还原迈克尔受体-亚烷基-β-酮酯和亚烷基-1,3-二酮的碳-碳双键，从而得到相应的饱和β-酮酯和1,3-二酮。该方法涉及铁催化的氢化硅烷化，然后原位水解甲硅烷基烯醇醚。最佳反应条件包括20 mol％的FeCl 3 ·6H 2室温下在二氯甲烷中加入O和三乙基硅烷。各种各样的底物以1、4选择性的方式还原，从而以极好的收率得到相应的饱和化合物。

  DOI：

  10.1016/j.tetlet.2018.07.041

文献信息

• Catalytic Enantioselective Protonation/Nucleophilic Addition of Diazoesters with Chiral Oxazaborolidinium Ion Activated Carboxylic Acids
  作者：Ki-Tae Kang、Seung Tae Kim、Geum-Sook Hwang、Do Hyun Ryu

  DOI：10.1002/anie.201612655

  日期：2017.3.27

  A new chiral Brønsted acid derived from carboxylic acid and a chiral oxazaborolidinium ion (COBI), as an activator, is introduced. This acid was successfully applied as a catalyst for the highly enantioselective protonation/nucleophilic addition of diazoesters with carboxylic acids.

  引入了一种新的手性布朗斯台德酸，其衍生自羧酸和手性恶唑硼烷鎓离子（COBI）作为活化剂。该酸已成功地用作重氮酸酯与羧酸的高度对映选择性质子化/亲核加成的催化剂。
• Desymmetrizing Asymmetric Ring Expansion of Cyclohexanones with α-Diazoacetates Catalyzed by Chiral Aluminum Lewis Acid
  作者：Takuya Hashimoto、Yuki Naganawa、Keiji Maruoka

  DOI：10.1021/ja202070j

  日期：2011.6.15

  in a 2:1 ratio was found to promote novel catalytic asymmetric ring expansion of cyclohexanone with α-substituted α-diazoacetates to give seven-membered rings with an all-carbon quaternary center. Application of this strategy to 4-substituted cyclohexanones opened up a novel way for the catalytic desymmetrizing asymmetric construction of cycloheptanones bearing remote α,δ-chiral centers.

  由 Me(3)Al 和 3,3'-双(三甲基甲硅烷基)-BINOL 以 2:1 的比例组成的手性铝路易斯酸催化剂被发现可促进环己酮与 α-取代的 α-重氮乙酸酯的新型催化不对称扩环，得到具有全碳四元中心的七元环。将该策略应用于 4-取代环己酮为带有远程 α,δ-手性中心的环庚酮的催化去对称不对称结构开辟了一条新途径。
• Catalytic Asymmetric Insertion of Diazoesters into Aryl-CHO Bonds: Highly Enantioselective Construction of Chiral All-Carbon Quaternary Centers
  作者：Lizhu Gao、Byung Chul Kang、Do Hyun Ryu

  DOI：10.1021/ja408196g

  日期：2013.10.2

  This paper describes a catalytic enantioselective route to synthesize functionalized all-carbon quaternary acyclic systems via a boron Lewis acid-promoted formal C-C insertion of diazoesters into aryl-CHO bonds. In the presence of chiral (S)-oxazaborolidinium cation 1d as a catalyst, the reaction proceeded in good yield (up to 83%) with good regioselectivity (up to 88:12) and excellent enantioselectivity

  本文描述了一种催化对映选择性路线，通过硼路易斯酸促进的重氮酯形式的 CC 插入芳基-CHO 键来合成功能化的全碳季无环系统。在手性 (S)-oxazaborolidinium 阳离子 1d 作为催化剂存在下，反应以良好的收率（高达 83%）、良好的区域选择性（高达 88:12）和优异的对映选择性（高达 99% ee）进行。该方法的合成潜力通过将产物转化为 α- 和 β- 氨基酯来说明。
• Improved Palladium-Catalysed Synthesis of α-Benzyl-β-keto Esters
  作者：Nicholas Bennett、Anne Goldby、Rachel Pringle

  DOI：10.1055/s-0030-1258095

  日期：2010.7

  This paper describes the development of an imporved protocol for the synthesis of α-benzyl-β-keto esters from aryl bromides via Heck reaction. The use of this protocol to synthesise a variety of diverse α-benzyl-β-keto esters for use in the preparation of new pharmaceutical agents is demonstrated.

  本文介绍了通过 Heck 反应从芳基溴化物合成 δ-苄基-δ-酮酯的改进方案。该方法可用于合成各种不同的δ-苄基-δ-酮酯，以制备新的药剂。
• Cyclization of Arylacetoacetates to Indene and Dihydronaphthalene Derivatives in Strong Acids. Evidence for Involvement of Further Protonation of O,O-Diprotonated β-Ketoester, Leading to Enhancement of Cyclization
  作者：Hiroaki Kurouchi、Hiromichi Sugimoto、Yuko Otani、Tomohiko Ohwada

  DOI：10.1021/ja908749u

  日期：2010.1.20

  The chemical features, such as substrate stability, product distribution, and substrate generality, and the reaction mechanism of Bronsted superacid-catalyzed cyclization reactions of aromatic ring-containing acetoacetates (beta-ketoesters) were examined in detail. While two types of carbonyl cyclization are possible, i.e., keto cyclization and ester cyclization, the former was found to take place exclusively. The reaction constitutes an efficient method to synthesize indene and 3,4-dihydronapthalene derivatives. Acid-base titration monitored with C-13 NMR spectroscopy showed that the acetoacetates are fully O-1,O-3-diprotonated at H-0 = -11. While the five-membered ring cyclization of the arylacetoacetates proceeded slowly at H-0 = -11, a linear increase in the rate of the cyclization was found with increasing acidity in the high acidity region of H-0 = -11.8 to -13.3. Therefore, the O-1,O-3-diprotonated acetoacetates exhibited some cyclizing reactivity, but they are not the reactive intermediates responsible for the acceleration of the cyclization in the high acidity region. The reactive cationic species might be formed by further protonation (or protosolvation) of the O-1,O-3-diprotonated acetoacetates; i.e., they may be tricationic species. Thermochemical data on the acid-catalyzed cyclization of the arylacetoacetates showed that the activation energy is decreased significantly as compared with that of the related acid-catalyzed cyclization reaction of a compound bearing a single functional group, such as a ketone. These findings indicate that intervention of the trication contributes to the activation of the cyclization of arylacetoacetates in strong acid, and the electron-withdrawing nature of the O-protonated ester functionality significantly increases the electrophilicity of the ketone moiety.