2-(3-methylbenzyl)-3-oxo-butyric acid methyl ester | 1203476-28-1

• 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: 2-(3-methylbenzyl)-3-oxo-butyric acid methyl ester
• 英文别名: Methyl 2-[(3-methylphenyl)methyl]-3-oxobutanoate
• CAS: 1203476-28-1
• 化学式: C₁₃H₁₆O₃
• 分子量: 220.268
• InChiKey: NZEGYUYPQSYAGV-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：

  2-(3-methylbenzyl)-3-oxo-butyric acid methyl ester 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， 生成 methyl 2-diazo-3-(m-tolyl)propanoate
  参考文献：
  名称：

  酮与α-烷基α-重氮酯的催化不对称同构

  摘要：

  酮与重氮化合物的同源性是合成单碳扩链无环酮或扩环环酮的有用策略。然而，由于较低的反应性和复杂的选择性，无环酮与α-重氮酯的不对称同源性仍然是一个挑战。在此，我们报道了利用手性scan（III）N，N与N -α-烷基α-重氮酯对苯乙酮和相关衍生物的对映选择性催化同源性'-二氧化物为路易斯酸催化剂。该反应提供了高度化学，区域和对映体选择性的途径，用于通过酮的高选择性烷基基团迁移来合成具有全碳季中心的旋光性β-酮酯。此外，环状酮的扩环是在稍微修饰的条件下完成的，从而提供了一系列对映体富集的环状β-酮酯。已经进行了密度泛函理论计算，以阐明可以解释所观察到的区域和对映选择性的反应途径和可能的工作模型。

  DOI：

  10.1021/jacs.0c12683
• 作为产物：
  描述：

  3-甲基苄溴 、 乙酰乙酸甲酯 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 12.5h， 生成 2-(3-methylbenzyl)-3-oxo-butyric acid methyl ester
  参考文献：
  名称：

  酮与α-烷基α-重氮酯的催化不对称同构

  摘要：

  酮与重氮化合物的同源性是合成单碳扩链无环酮或扩环环酮的有用策略。然而，由于较低的反应性和复杂的选择性，无环酮与α-重氮酯的不对称同源性仍然是一个挑战。在此，我们报道了利用手性scan（III）N，N与N -α-烷基α-重氮酯对苯乙酮和相关衍生物的对映选择性催化同源性'-二氧化物为路易斯酸催化剂。该反应提供了高度化学，区域和对映体选择性的途径，用于通过酮的高选择性烷基基团迁移来合成具有全碳季中心的旋光性β-酮酯。此外，环状酮的扩环是在稍微修饰的条件下完成的，从而提供了一系列对映体富集的环状β-酮酯。已经进行了密度泛函理论计算，以阐明可以解释所观察到的区域和对映选择性的反应途径和可能的工作模型。

  DOI：

  10.1021/jacs.0c12683

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。
• 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.
• Catalytic Asymmetric Homologation of Ketones with α-Alkyl α-Diazo Esters
  作者：Fei Tan、Maoping Pu、Jun He、Jinzhao Li、Jian Yang、Shunxi Dong、Xiaohua Liu、Yun-Dong Wu、Xiaoming Feng

  DOI：10.1021/jacs.0c12683

  日期：2021.2.10

  derivatives with α-alkyl α-diazo esters utilizing a chiral scandium(III) N,N′-dioxide as the Lewis acid catalyst. This reaction supplies a highly chemo-, regio-, and enantioselective pathway for the synthesis of optically active β-keto esters with an all-carbon quaternary center through highly selective alkyl-group migration of the ketones. Moreover, the ring expansion of cyclic ketones was accomplished under

  酮与重氮化合物的同源性是合成单碳扩链无环酮或扩环环酮的有用策略。然而，由于较低的反应性和复杂的选择性，无环酮与α-重氮酯的不对称同源性仍然是一个挑战。在此，我们报道了利用手性scan（III）N，N与N -α-烷基α-重氮酯对苯乙酮和相关衍生物的对映选择性催化同源性'-二氧化物为路易斯酸催化剂。该反应提供了高度化学，区域和对映体选择性的途径，用于通过酮的高选择性烷基基团迁移来合成具有全碳季中心的旋光性β-酮酯。此外，环状酮的扩环是在稍微修饰的条件下完成的，从而提供了一系列对映体富集的环状β-酮酯。已经进行了密度泛函理论计算，以阐明可以解释所观察到的区域和对映选择性的反应途径和可能的工作模型。