methyl 2-benzyl-3-oxo-3-phenylpropanoate | 94083-39-3

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 直链 1,3-二芳基丙烷
• 英文名称: methyl 2-benzyl-3-oxo-3-phenylpropanoate
• CAS: 94083-39-3
• 化学式: C₁₇H₁₆O₃
• 分子量: 268.312
• InChiKey: SYSKVHOILAQODE-UHFFFAOYSA-N

物化性质

• 沸点：
  344.5±9.0 °C(Predicted)
• 密度：
  1.141±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 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-benzyl-3-oxo-3-phenylpropanoate 在 一水合肼 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 12.0h， 以76%的产率得到4-benzyl-5-phenyl-2,3-dihydro-1H-pyrazol-3-one
  参考文献：
  名称：

  Morita–Baylis–Hillman adducts as building blocks of heterocycles: a simple approach to 4-substituted pyrazolones, and mechanism investigation via ESI–MS(/MS)

  摘要：

  We describe herein an efficient approach for the preparation of 4-substituted 2,3-dihydro-1H-pyrazol-3-ones starting from Morita-Baylis-Hillman adducts. These heterocycles were obtained in two or three steps as single isomers with moderate to good overall yields. One efficient and alternative methodology for the synthesis of alpha-methyl-beta-ketoesters is also reported (up to 91 % yield). Additionally, the mechanism of formation of pyrazolones was investigated employing ESI-MS/MS reaction monitoring.

  DOI：

  10.1007/s00706-015-1427-6
• 作为产物：
  描述：

  苯丙炔酸甲酯 在 sodium hydride 作用下， 以 1,4-二氧六环 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 methyl 2-benzyl-3-oxo-3-phenylpropanoate
  参考文献：
  名称：

  Synthesis of .beta.-Dicarbonyl Compounds via the Conjugate Addition of Benzaldoximate Anion to .alpha.,.beta.-Acetylenic Carbonyl Compounds

  摘要：

  DOI：

  10.1021/jo00084a051

文献信息

• Catalytic TMSCl promoted powerful aldol addition and Claisen condensation mediated by TiCl4/Bu3N agent: comparison and evaluation with the Mukaiyama aldol addition
  作者：Yoshihiro Yoshida、Noriaki Matsumoto、Ryota Hamasaki、Yoo Tanabe

  DOI：10.1016/s0040-4039(99)00682-6

  日期：1999.5

  catalyst (0.05 equiv) signifiantly promoted the TiCl4/Bu3N-mediated direct cross aldol additions of sterically crowded ketones and α-hetero substituted ketones, and also the direct Claisen condensation between methyl esters.

  MSCl催化剂（0.05当量）显着促进了空间拥挤的酮和α-杂取代的酮的TiCl 4 / Bu 3 N介导的直接交叉羟醛加成，以及甲酯之间的直接Claisen缩合。
• TiCl4/Bu3N/(catalytic TMSOTf): Efficient agent for direct aldol addition and Claisen condensation
  作者：Yoshihiro Yoshida、Ryosuke Hayashi、Hiromasa Sumihara、Yoo Tanabe

  DOI：10.1016/s0040-4039(97)10320-3

  日期：1997.12

  efficient cross aldol additions between different ketones and between ketones and aldehydes, in good to excellent yields with high syn-stereoselectivities. As an extension, direct Claisen condensation between methyl esters was also promoted by TiCl4/Bu3N with 0.05 equiv of TMSOTf co-catalyst.

  的TiCl 4 /卜3 Ñ进行不同酮类之间和酮和醛，在良好的以高优异的产率之间高效交叉醛醇添加顺-stereoselectivities。此外，TiCl 4 / Bu 3 N与0.05当量的TMSOTf助催化剂还促进了甲酯之间的直接Claisen缩合反应。
• Enantioselective and Diastereoselective Ir-Catalyzed Hydrogenation of α-Substituted β-Ketoesters via Dynamic Kinetic Resolution
  作者：Guoxian Gu、Jiaxiang Lu、Ouran Yu、Jialin Wen、Qin Yin、Xumu Zhang

  DOI：10.1021/acs.orglett.8b00433

  日期：2018.4.6

  An iridium/f-amphol catalytic system for the enantioselective hydrogenation of α-substituted β-ketoesters via dynamic kinetic resolution is reported. The desired anti products were obtained in high yields (up to 98%) with good diastereoselectivity (up to 96:4 diastereometic ratio (dr)) and excellent enantioselectivity (up to >99% enantiomeric excess (ee)). A catalytic model is proposed to explain the

  报道了用于通过动态动力学拆分对α-取代的β-酮酸酯进行对映选择性氢化的铱/ f-amphol催化体系。以高收率（高达98％），良好的非对映选择性（高达96：4的非对映比率（dr））和优异的对映选择性（高达> 99％的对映体过量（ee））获得所需的抗产物。提出了催化模型来解释立体选择性。
• Sterically Hindered Chiral Ferrocenyl P,N,N-Ligands for Highly Diastereo-/Enantioselective Ir-Catalyzed Hydrogenation of α-Alkyl-β-ketoesters via Dynamic Kinetic Resolution
  作者：Chuan-Jin Hou、Xiang-Ping Hu

  DOI：10.1021/acs.orglett.6b02828

  日期：2016.11.4

  A new class of sterically hindered chiral ferrocenyl P,N,N-ligands have been prepared through a two-step transformation from (Sc,Rp)-PPFNH2, in which a new (R)-stereogenic center at the pyridinylmethyl position was generated in high diastereoselectivity. With these newly developed P,N,N-ligands, Ir-catalyzed asymmetric hydrogenation of various α-alkyl-substituted β-aryl-β-ketoesters via dynamic kinetic

  通过从（S c，R p）-PPFNH 2的两步转化制备了新型的空间位阻性手性二茂铁基二茂铁基P，N，N-配体，其中在吡啶基甲基位置上有一个新的（R）-立体异构中心产生的非对映异构体选择性高。借助这些新开发的P，N，N配体，首次在高非对映体和对映体选择性下，通过动态动力学拆分实现了Ir催化的各种α-烷基取代的β-芳基-β-酮酸酯的不对称氢化，导致了多种光学活性的反-β-羟基酯含量高达99％ee。研究表明，这些配体的吡啶基甲基位置上的额外立体中心对于实现这种氢化作用至关重要。
• The first successful intermolecular Heck reaction of Baylis–Hillman adducts: synthesis of β-aryl substituted Baylis–Hillman adducts
  作者：Jeong Mi Kim、Ko Hoon Kim、Taek Hyeon Kim、Jae Nyoung Kim

  DOI：10.1016/j.tetlet.2008.03.102

  日期：2008.5

  The first successful intermolecular Heck reaction between Baylis–Hillman adducts and aryl iodides was achieved under the conditions comprising Pd(OAc)2/n-Bu4NBr/KOAc in CH3CN.

  在包括CH 3 CN中的Pd（OAc）2 / n -Bu 4 NBr / KOAc的条件下，成功实现了Baylis-Hillman加合物和碘代芳基化合物之间的第一个成功的分子间Heck反应。