3-oxobutyl 4-methoxybenzoate | 29342-30-1

• 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: 3-oxobutyl 4-methoxybenzoate
• 英文别名: 3-Oxobutyl 4-methoxybenzoate
• CAS: 29342-30-1
• 化学式: C₁₂H₁₄O₄
• 分子量: 222.241
• InChiKey: ZKAJFBWRYGVAEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  3-oxobutyl 4-methoxybenzoate 、 (1S,2S)-N-(trifluoroacetyl)norpseudoephedrine trimethylsilyl ether 、 烯丙基三甲基硅烷 在 三氟甲磺酸 、 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 反应 96.0h， 生成 4-Methoxy-benzoic acid (R)-3-methyl-3-[(1S,2S)-1-phenyl-2-(2,2,2-trifluoro-acetylamino)-propoxy]-hex-5-enyl ester 、 4-Methoxy-benzoic acid (S)-3-methyl-3-[(1S,2S)-1-phenyl-2-(2,2,2-trifluoro-acetylamino)-propoxy]-hex-5-enyl ester
  参考文献：
  名称：

  Synthesis of Enantiopure Homoallylic Alcohols

  摘要：

  A highly selective asymmetric domino allylation of aliphatic ketones is described. When methyl ketones 1a-g, the chiral trimethylsilyl ether 2, and allylsilane 3 react in the presence of catalytic amounts of trifluoromethanesulfonic acid, the homoallylic ethers 4a-g are produced with up to 24:1 diastereoselectivity and 89% yield. Cleavage of the obtained tertiary homoallylic ethers C using lithium or sodium in liquid ammonia gives the homoallytic alcohols 5 in 75 to 95% yield and up to 92% ee. Even ethyl methyl ketone 1a, the most difficult example, showed a stereoselectivity of 9:1 at -78 degrees C and 24:1 at -109 degrees C. In addition, the allylation of protected hydroxyalkyl methyl ketones 7a-j was investigated to give the corresponding homoallylic ethers 8a-j with a diastereoselectivity of up to >24:1 and 98% yield. In contrast, ethyl alkyl ketones 1h-j have a low selectivity.

  DOI：

  10.1002/(sici)1521-3765(19980904)4:9<1862::aid-chem1862>3.0.co;2-c
• 作为产物：
  描述：

  4-羟基-2-丁酮 、 对甲氧基苯甲酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 生成 3-oxobutyl 4-methoxybenzoate
  参考文献：
  名称：

  Base-catalyzed .beta.-elimination reactions in aqueous solution. IV. Elimination from 4-(4-substituted benzoyloxy)-2-butanones

  摘要：

  DOI：

  10.1021/ja00718a023

文献信息

• A Nucleophilic Activation of Carboxylic Acids by Proline: Oxa-Michael Addition to Methyl Vinyl Ketone under Solvent-Free Conditions
  作者：Srinivasan Easwar、Ajit Jha、Heena Inani

  DOI：10.1055/s-0036-1588172

  日期：2017.7

  chromatographic purification, imparting a green quotient to the protocol. A heterodimeric non-covalent interaction between the amino acid and the carboxylic acid appears to be the most plausible mechanistic interpretation for the nucleophilic activation; additionally, the possible activation of the Michael acceptor by iminium ion formation presents an interesting case of proline acting as a bifunctional catalyst

  脯氨酸对羧酸的偶然亲核活化有助于在 60°C 下在无溶剂条件下实现甲基乙烯基酮的直接加氢羧化。在这种 oxa-Michael 加成中成功使用了多种羧酸，以中等产率提供了有用的 4-酰氧基-2-丁酮。反应在无溶剂条件下进行，产物通过简单的后处理程序以高纯度分离，无需任何柱色谱纯化，为方案赋予绿色商数。氨基酸和羧酸之间的异二聚体非共价相互作用似乎是亲核活化最合理的机制解释。此外，
• Gold N‐Heterocyclic Carbene Catalysts for the Hydrofluorination of Alkynes Using Hydrofluoric Acid: Reaction Scope, Mechanistic Studies and the Tracking of Elusive Intermediates
  作者：Raphaël Gauthier、Nikolaos V. Tzouras、Ziyun Zhang、Sandrine Bédard、Marina Saab、Laura Falivene、Kristof Van Hecke、Luigi Cavallo、Steven P. Nolan、Jean‐François Paquin

  DOI：10.1002/chem.202103886

  日期：2022.1.19

  Unconventional fluorination: The development of the chemoselective gold-catalysed hydrofluorination of terminal alkynes using aqueous HF and an easily accessible N-heterocyclic carbene-gold pre-catalyst is reported. Following the observation and isolation of unprecedented organometallic intermediates and computational studies, a catalytic cycle is proposed, featuring an in situ generation of the chemoselective

  非常规氟化：报道了使用 HF 水溶液和易于获得的 N-杂环卡宾-金预催化剂对末端炔烃进行化学选择性金催化氢氟化反应。在观察和分离前所未有的有机金属中间体和计算研究之后，提出了一种催化循环，其特点是原位生成化学选择性催化剂。
• Synthesis of Enantiopure Homoallylic Alcohols
  作者：Lutz F. Tietze、Kai Schiemann、Christoph Wegner、Christian Wulff

  DOI：10.1002/(sici)1521-3765(19980904)4:9<1862::aid-chem1862>3.0.co;2-c

  日期：1998.9.4

  A highly selective asymmetric domino allylation of aliphatic ketones is described. When methyl ketones 1a-g, the chiral trimethylsilyl ether 2, and allylsilane 3 react in the presence of catalytic amounts of trifluoromethanesulfonic acid, the homoallylic ethers 4a-g are produced with up to 24:1 diastereoselectivity and 89% yield. Cleavage of the obtained tertiary homoallylic ethers C using lithium or sodium in liquid ammonia gives the homoallytic alcohols 5 in 75 to 95% yield and up to 92% ee. Even ethyl methyl ketone 1a, the most difficult example, showed a stereoselectivity of 9:1 at -78 degrees C and 24:1 at -109 degrees C. In addition, the allylation of protected hydroxyalkyl methyl ketones 7a-j was investigated to give the corresponding homoallylic ethers 8a-j with a diastereoselectivity of up to >24:1 and 98% yield. In contrast, ethyl alkyl ketones 1h-j have a low selectivity.
• Base-catalyzed .beta.-elimination reactions in aqueous solution. IV. Elimination from 4-(4-substituted benzoyloxy)-2-butanones
  作者：Richard C. Cavestri、Leo R. Fedor

  DOI：10.1021/ja00718a023

  日期：1970.7