1,1-dimethylethyl 2-methylene-3-oxo-3-phenylpropanoate | 135514-05-5

• 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: 1,1-dimethylethyl 2-methylene-3-oxo-3-phenylpropanoate
• 英文别名: t-butyl α-benzoylacrylate；tert-butyl 2-benzoylacrylate；Tert-butyl 2-benzoylprop-2-enoate
• CAS: 135514-05-5
• 化学式: C₁₄H₁₆O₃
• 分子量: 232.279
• InChiKey: IFBMNOJLFIPTMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  1,1-dimethylethyl 2-methylene-3-oxo-3-phenylpropanoate 在 水 作用下， 以 丙酮 为溶剂， 反应 72.0h， 以44%的产率得到1,1-dimethylethyl 2-hydroxymethyl-3-oxo-3-phenylpropanoate
  参考文献：
  名称：

  Hoffmann, H. Martin R.; Gassner, Andreas; Eggert, Ulrike, Chemische Berichte, 1991, vol. 124, # 11, p. 2475 - 2480

  摘要：

  DOI：
• 作为产物：
  描述：

  tert-butyl 2-(hydroxy(phenyl)methyl)acrylate 在 2-碘酰基苯甲酸 作用下， 以 乙腈 为溶剂， 生成 1,1-dimethylethyl 2-methylene-3-oxo-3-phenylpropanoate
  参考文献：
  名称：

  Morita-Baylis-Hillman 酮的酰基转移驱动的 Rauhut-Currier 二聚化

  摘要：

  在 DABCO 存在的情况下，观察到源自 Morita-Baylis-Hillman 加合物的 1,1-二取代活化烯烃的偶然 Rauhut-Currier 二聚反应。该反应由酰基的迁移驱动，并在大多数情况下产生多官能化的烯醇酯，产率大于 90%，无需柱层析纯化。酰基转移被认为是通过典型的 Morita-Baylis-Hillman (MBH) 反应的过渡态进行的，并得到涉及计算计算的简短机理研究的支持。

  DOI：

  10.1021/acs.joc.2c02244

文献信息

• Noncovalent Organocatalytic Synthesis of Enantioenriched Terminal Aziridines with a Quaternary Stereogenic Center
  作者：Claudia De Fusco、Tiziana Fuoco、Gianluca Croce、Alessandra Lattanzi

  DOI：10.1021/ol3017066

  日期：2012.8.17

  A high-yielding and enantioselective access to novel N-Boc terminal aziridines, bearing a quaternary stereogenic center, has been developed via an aza-Michael initiated ring-closure (aza-MIRC) reaction of α-acyl acrylates with an N-tosyloxy tert-butyl carbamate catalyzed by a chiral amino thiourea. The feasibility of the aziridine regioselective ring-opening to valuable α,α-disubstituted α-amino acid

  通过α-丙烯酸丙烯酸酯与N-甲苯磺酰氧基叔胺的氮杂-迈克尔引发的闭环反应（aza-MIRC），开发了具有新型立体构型中心的新型N- Boc末端氮丙啶的高产和对映选择性的方法。氨基氨基硫脲催化氨基甲酸丁酯。已经证明了氮丙啶区域选择性开环成有价值的α，α-二取代的α-氨基酸酯的可行性。
• Highly Chemoselective Rauhut–Currier Reaction between Maleimides and Enones and Dual Phosphine-Mediated One-Pot Synthesis of Bicyclic and Polycyclic Skeletons
  作者：Rong Zhou、Jianfang Wang、Jia Yu、Zhengjie He

  DOI：10.1021/jo401363u

  日期：2013.11.1

  A highly chemoselective phosphine-catalyzed Rauhut–Currier reaction between maleimides and enones has been realized under very mild conditions, affording the corresponding cross-coupling products in moderate to excellent yields. On the basis of this reaction, an efficient dual phosphine-mediated one-pot synthesis of bicyclic and polycyclic compounds containing a cyclopenta[c]pyrrole skeleton has been

  在非常温和的条件下已实现了高度化学选择性的膦催化的马来酰亚胺和烯酮之间的Rauhut-Currier反应，从而以中等至极好的收率提供了相应的交叉偶联产物。在此反应的基础上，据此开发了一种有效的双膦介导的一锅合成含环戊五烯[ c ]吡咯骨架的双环和多环化合物的方法，其特征是分子间Rauhut-Currier反应和分子内Wittig反应的串联序列。
• Diethyl phosphite mediated reductive [1 + 4] annulation of α-ketoesters with α, β-unsaturated ketones and synthesis of polysubstituted 2,3-dihydrofurans
  作者：Feixue Xue、Xiangyu Chen、Zhengjie He

  DOI：10.1016/j.tet.2022.132646

  日期：2022.1

  A diethyl phosphite mediated reductive [1 + 4] annulation of α-ketoesters with α, β-unsaturated ketones has been developed, which provides an effective and simple method to prepare polysubstituted 2,3-dihydrofurans bearing a quaternary carbon center in fair to excellent yields. In the reaction, the in situ generated [1,2]-phospha-Brook rearrangement adduct of phosphite and α-ketoester presumably serves

  开发了一种亚磷酸二乙酯介导的α-酮酯与α, β-不饱和酮的还原[1 + 4]环化反应，为制备具有季碳中心的多取代2,3-二氢呋喃提供了一种有效且简单的方法。产量。在该反应中，原位生成的亚磷酸酯和α-酮酯的[1,2]-phospha-Brook重排加合物可能作为C1合成子。因此，这项工作补充了 [1 + 4] 环化反应中磷试剂介导的 C1 合成子源。
• Mechanistic Investigations on the Interaction of Morita–Baylis–Hillman Ketones with 2-Aminothiophenol
  作者：Rajkiran Kumari、Ajit Kumar Jha、Akram Gulam Hussain Khan、Srinivasan Easwar

  DOI：10.1021/acs.joc.3c02993

  日期：2024.5.17

  of Morita–Baylis–Hillman ketones with 2-aminothiophenol mediated by Cs2CO3 results in an oxidative cyclization to 2,2-disubstituted dihydro-1,4-benzothiazines, with the structure of the product indicating the occurrence of an aza-Michael addition along the pathway. In contrast, in the absence of a base, the parent compounds interact to produce a thia-Michael adduct instead. A deeper mechanistic study

  Morita-Baylis-Hillman 酮与 2-氨基苯硫酚在 Cs 2 CO 3介导下的反应导致氧化环化为 2,2-二取代的二氢-1,4-苯并噻嗪，产物的结构表明氮杂的发生-迈克尔沿着路径添加。相反，在不存在碱的情况下，母体化合物相互作用产生硫杂-迈克尔加合物。更深入的机制研究提高了我们对明显矛盾的理解，并提供了对反应性依赖于碱基的转换的见解。
• Catalyst-Free Conjugate Addition of Indolizines to <i>In Situ</i>-Generated Oxidized Morita–Baylis–Hillman Adducts
  作者：Thiago S. Silva、Lucas A. Zeoly、Fernando Coelho

  DOI：10.1021/acs.joc.0c00189

  日期：2020.4.17

  Sequential one-pot 2-iodoxybenzoic acid (IBX) oxidation of Morita-Baylis-Hillman (MBH) adducts followed by catalyst-free indolizine conjugate addition was developed. The wide scopes of MBH adducts and indolizines were investigated, and densely functionalized adducts were obtained in yields of up to 94%. The conjugate addition step occurred in less than a minute at room temperature with total regioselectivity toward indolizine C3 carbon. Less nucleophilic C1 carbon was also alkylated when C3-substituted indolizines were employed as the substrate.