(E)-1,2-diphenylethanone O-methyl oxime | 163586-90-1

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 二苯乙烯类
• 英文名称: (E)-1,2-diphenylethanone O-methyl oxime
• 英文别名: (E)-N-methoxy-1,2-diphenylethanimine
• CAS: 163586-90-1
• 化学式: C₁₅H₁₅NO
• 分子量: 225.29
• InChiKey: OSPPVFVDJJCMGE-FOCLMDBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  21.6
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1,2-diphenylethanone O-methyl oxime 在 N-溴代丁二酰亚胺(NBS) 、 氨 作用下， 以 四氯化碳 、 二氯甲烷 为溶剂， 反应 8.0h， 生成 (E)-2-amino-1,2-diphenylethanone O-methyloxime
  参考文献：
  名称：

  Shatzmiller, Shimon; Bercovici, Sorin, Liebigs Annalen der Chemie, 1992, # 10, p. 1005 - 1010

  摘要：

  DOI：
• 作为产物：
  描述：

  alpha-氯乙酰苯 在 四(三苯基膦)钯 、 硫酸 、 cesium fluoride 作用下， 以 四氢呋喃 、 乙醇 为溶剂， 反应 3.0h， 生成 (E)-1,2-diphenylethanone O-methyl oxime
  参考文献：
  名称：

  钯催化的α-卤代甲基肟醚的铃木-宫浦交叉偶联和二卤代衍生物的位点选择性交叉偶联

  摘要：

  AbstractThe cross‐coupling reaction of chloro‐ and bromomethyl oxime ethers with a wide range of aryl‐, heteroaryl‐ and vinylboronic acids in the presence of catalytic palladium complexes with different phosphines has been carried out with good yields (60–98%, 40 examples). Regioselective cross‐coupling reactions differentiating between an alkyl or aryl position are achieved from dihalo oxime ethers containing Csp2‐ and Csp3‐halogen bonds using mono‐ or dicoordinated palladium catalysts such as Pd(dba)2/P(o‐tolyl)3 or Pd(PPh3)4. The selective orthogonal functionalization of dihalo oxime ethers is also described. Site‐selective transformations allow the introduction of the biaryl motif into dihalo oxime ethers preserving the highly activated alkyl halide moiety vicinal to the oxime group for further transformations. In this context, Z‐ and E‐oxime ethers could be considered as synthetic equivalents of ketones in palladium‐catalyzed Suzuki reactions.magnified image

  DOI：

  10.1002/adsc.201300444

文献信息

• Palladium-catalyzed C–H activation/C–C cross-coupling reactions via electrochemistry
  作者：Cong Ma、Chuan-Qi Zhao、Yi-Qian Li、Li-Pu Zhang、Xue-Tao Xu、Kun Zhang、Tian-Sheng Mei

  DOI：10.1039/c7cc07429h

  日期：——

  Palladium-catalyzed C–H activation/C–C cross-coupling reactions have emerged as attractive tools for organic synthesis. Typically, these reactions require stoichiometric chemical oxidants and exogenous ligands to regenerate the palladium catalyst and promote reductive elimination respectively. However, there are significant disadvantages associated with the use of traditional stoichiometric oxidants

  钯催化的C–H活化/ C–C交叉偶联反应已成为有机合成的诱人工具。通常，这些反应需要化学计量的化学氧化剂和外源性配体以分别再生钯催化剂并促进还原消除。然而，使用传统的化学计量的氧化剂存在显着的缺点，包括原子经济性差，副产物形成和高成本。为了克服这些问题，我们开发了一种电化学策略，利用PdII的阳极氧化来诱导选择性的C–C还原消除，从而分别使用硼试剂和α-酮酸实现甲基化和酰化。
• Diaryliodoniums by Rhodium(III)-Catalyzed CH Activation: Mild Synthesis and Diversified Functionalizations
  作者：Fang Xie、Zhipeng Zhang、Xinzhang Yu、Guodong Tang、Xingwei Li

  DOI：10.1002/anie.201502278

  日期：2015.6.15

  Diaryliodonium salts play an increasingly important role as an aryl source. Reported is the first synthesis of diaryliodoniums by rhodium(III)‐catalyzed CH hyperiodination of electron‐poor arenes under chelation assistance. This CI coupling reaction occurred at room temperature with high regio‐selectivity and functional‐group compatibility. Subsequent diversified nucleophilic functionalization of

  二芳基碘鎓盐作为芳基源发挥着越来越重要的作用。报道是由铑diaryliodoniums的第一合成（III）催化Ç 轰下螯合援助贫电子芳烃的hyperiodination。这种CI偶联反应在室温下具有较高的区域选择性和官能团相容性。随后对二芳基碘的多样化亲核官能化使得可以容易地构建CC，CN，CO，CS，CP和CBr键，并且在所有情况下，初始功能化均发生在含有螯合剂的芳烃上-团体。
• Rhodium(III)-Catalyzed Diastereoselective Ring-Opening of 7-Azabenzonorbornadienes with Aromatic Ketoximes: Synthesis of Benzophenanthridine Derivatives
  作者：Varathan Vinayagam、Arumugam Mariappan、Mrinmoy Jana、Masilamani Jeganmohan

  DOI：10.1021/acs.joc.9b02582

  日期：2019.12.6

  A rhodium(III)-catalyzed redox-neutral ring-opening of 7-azabenzonorbornadienes with aromatic ketoximes giving 2-arylated hydronaphthylamines in a highly diastereoselective manner is described. Later, the 2-arylated hydronaphthylamines were converted into highly sensitive 13,14-dehydro benzophenanthridine derivatives by HCl hydrolysis. Further, 13,14-dehydro benzophenanthridines were aromatized into

  描述了铑（III）催化的7-氮杂苯并降冰片二烯与芳族酮肟的氧化还原-中性开环，以高度非对映选择性的方式产生2-芳基氢化萘胺。随后，通过HCl水解将2-芳基化的萘胺转化为高度敏感的13,14-脱氢苯并菲衍生物。此外，在DDQ存在下，将13,14-脱氢苯并菲衍生物芳香化为生物学上重要的苯并菲衍生物。提出了一种可能的反应机理，并得到了氘标记研究和Rhodacycle中间体的分离的支持。
• Palladium-Catalyzed Suzuki Carbonylative Reaction of α-Halomethyl Oxime Ethers: A Regioselective Route to Unsymmetrical 1,3-Oxyiminoketones
  作者：Bárbara Noverges、Mercedes Medio-Simón、Gregorio Asensio

  DOI：10.1002/adsc.201400442

  日期：2014.11.24

  AbstractThe three‐component reaction of α‐halomethyl oxime ethers, boronic acids and carbon monoxide at atmospheric pressure catalyzed by tetrakis(triphenylphosphine)palladium(0) gives efficiently unsymmetrical β‐alkoxyimino carbonyl compounds with total control of the regioselectivity, in high yield and atomic economy. Simple commercially available starting materials are used in this synthetic procedure. The three components assembly takes place preferentially versus the competing direct coupling or other possible side reactions. The mechanism of the transformation was investigated by NMR and intermediate palladium(II) complexes were detected.magnified image
• Palladium-Catalyzed Suzuki-Miyaura Cross-Coupling of α-Halomethyl Oxime Ethers and Site-Selective Cross-Coupling of Dihalo Derivatives
  作者：Bárbara Noverges、Cristian Mollar、Mercedes Medio-Simón、Gregorio Asensio

  DOI：10.1002/adsc.201300444

  日期：2013.8.12

  AbstractThe cross‐coupling reaction of chloro‐ and bromomethyl oxime ethers with a wide range of aryl‐, heteroaryl‐ and vinylboronic acids in the presence of catalytic palladium complexes with different phosphines has been carried out with good yields (60–98%, 40 examples). Regioselective cross‐coupling reactions differentiating between an alkyl or aryl position are achieved from dihalo oxime ethers containing Csp2‐ and Csp3‐halogen bonds using mono‐ or dicoordinated palladium catalysts such as Pd(dba)2/P(o‐tolyl)3 or Pd(PPh3)4. The selective orthogonal functionalization of dihalo oxime ethers is also described. Site‐selective transformations allow the introduction of the biaryl motif into dihalo oxime ethers preserving the highly activated alkyl halide moiety vicinal to the oxime group for further transformations. In this context, Z‐ and E‐oxime ethers could be considered as synthetic equivalents of ketones in palladium‐catalyzed Suzuki reactions.magnified image