(E)-1-chloropropan-2-one O-benzyl oxime

• 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: (E)-1-chloropropan-2-one O-benzyl oxime
• 英文别名: (E)-1-chloropropan-2-one O-benzyloxime；(E)-chloroacetone O-benzyloxime；(E)-1-chloro-N-phenylmethoxypropan-2-imine
• 化学式: C₁₀H₁₂ClNO
• 分子量: 197.664
• InChiKey: BPWUEERMGRVEON-FMIVXFBMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  4-甲氧基苯硼酸 、 (E)-1-chloropropan-2-one O-benzyl oxime 在 四(三苯基膦)钯 、 cesium fluoride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 以82%的产率得到
  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
• 作为产物：
  描述：

  苄氧基胺盐酸盐 、 一氯丙酮 在 硫酸 作用下， 以 乙醇 为溶剂， 以90%的产率得到(E)-1-chloropropan-2-one O-benzyl oxime
  参考文献：
  名称：

  钯催化的α-卤代甲基肟醚的Suzuki羰基化反应：向不对称1,3-Oxyiminoketones的区域选择性路线。

  摘要：

  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

  DOI：

  10.1002/adsc.201400442

文献信息

• Stannyl Radical Addition-Cyclization of Oxime Ethers Connected with Olefins
  作者：Hideto Miyabe、Hirotaka Tanaka、Takeaki Naito

  DOI：10.1248/cpb.52.74

  日期：——

  Stannyl radical addition-cyclization of oxime ethers connected with olefin moieties was studied. The radical reactions proceeded effectively by the use of triethylborane as a radical initiator to provide the functionalized pyrrolidines via a carbon–carbon bond-forming process.

  研究了与烯烃分子相连的肟醚的斯坦尼基加成-环化反应。使用三乙基硼烷作为自由基引发剂，通过碳-碳键形成过程提供官能化的吡咯烷，从而有效地进行自由基反应。
• Verfahren zur Herstellung von alpha-Chlorketoximethern
  申请人：BASF Aktiengesellschaft

  公开号：EP0052742A1

  公开（公告）日：1982-06-02

  Herstellung von α-Chlorketoximethern durch Umsetzung von a-Chlorketonen mit Oximethern in Gegenwart von Säure. Die nach dem Verfahren der Erfindung herstellbaren a-Chlorketoximethern sind wertvolle Ausgangsstoffe für die Herstellung von Farbstoffen, Pharmazeutika und Schädlingsbekämpfungsmitteln.

  在酸存在下，通过 a-氯酮与肟醚反应制备 α-氯酮肟醚。 通过本发明的工艺可以制得的 a-氯酮肟醚是生产染料、药品和杀虫剂的重要起始原料。
• SEVERIN, T.;LERCHE, H., SYNTHESIS, BRD, 1982, N 4, 305-307
  作者：SEVERIN, T.、LERCHE, H.

  DOI：——

  日期：——
• 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
• 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