(E)-1-(4-chlorophenyl)ethanone O-benzyl oxime | 937371-83-0

• 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-(4-chlorophenyl)ethanone O-benzyl oxime
• 英文别名: (E)-1-(4-chlorophenyl)ethan-1-one O-benzyl oxime；(E)-1-(4-chlorophenyl)-N-phenylmethoxyethanimine
• CAS: 937371-83-0
• 化学式: C₁₅H₁₄ClNO
• 分子量: 259.735
• InChiKey: VTNUTAJGHHKVAK-SFQUDFHCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  18
• 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-(4-chlorophenyl)ethanone O-benzyl oxime 在 C₉H₁₆BNO 、 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 反应 48.0h， 以91%的产率得到(R)-(+)-1-(4-氯苯基)乙胺
  参考文献：
  名称：

  Enantioselective reduction of ketoxime ethers with borane–oxazaborolidines and synthesis of the key intermediate leading to (S)-rivastigmine

  摘要：

  The reduction of representative alkyl aryl (E)-ketoxime O-benzyl ethers with borane catalyzed by terpene oxazaborolidines, derived from (1R)-nopinone and (1R)-camphor, gave the corresponding amines with 82-99% ee. Oxazaborolidines derived from (1S)-2-carene and (1S)-3-carene were less selective. (S)-1-(3-Methoxyphenyl)ethanamine (94% ee) the key intermediate in the synthesis of (S)-rivastigmine, was obtained by the reduction of (E)-1-(3-methoxyphenyl)ethanone O-benzyl oxime with borane/oxazaborolidine generated from (S)-valinol. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.05.008
• 作为产物：
  描述：

  对氯苯乙酮 在 盐酸羟胺 、 sodium acetate 、 sodium hydride 作用下， 以 乙醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 29.0h， 生成 (E)-1-(4-chlorophenyl)ethanone O-benzyl oxime
  参考文献：
  名称：

  Enantioselective reduction of ketoxime ethers with borane–oxazaborolidines and synthesis of the key intermediate leading to (S)-rivastigmine

  摘要：

  The reduction of representative alkyl aryl (E)-ketoxime O-benzyl ethers with borane catalyzed by terpene oxazaborolidines, derived from (1R)-nopinone and (1R)-camphor, gave the corresponding amines with 82-99% ee. Oxazaborolidines derived from (1S)-2-carene and (1S)-3-carene were less selective. (S)-1-(3-Methoxyphenyl)ethanamine (94% ee) the key intermediate in the synthesis of (S)-rivastigmine, was obtained by the reduction of (E)-1-(3-methoxyphenyl)ethanone O-benzyl oxime with borane/oxazaborolidine generated from (S)-valinol. (C) 2012 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2012.05.008

文献信息

• Asymmetric Synthesis of Primary Amines via the Spiroborate-Catalyzed Borane Reduction of Oxime Ethers
  作者：Xiaogen Huang、Margarita Ortiz-Marciales、Kun Huang、Viatcheslav Stepanenko、Francisco G. Merced、Angel M. Ayala、Wildeliz Correa、Melvin De Jesús

  DOI：10.1021/ol0704791

  日期：2007.4.1

  enantioselective borane reduction of O-benzyloxime ethers to primary amines was studied under catalytic conditions using the spiroborate esters 5-10 derived from nonracemic 1,2-amino alcohols and ethylene glycol. Effective catalytic conditions were achieved using only 10% of catalyst 5 derived from diphenylvalinol in dioxane at 0 degrees C resulting in complete conversion to the corresponding primary amine in

  [反应：见正文]在催化条件下，使用衍生自非外消旋1，2-氨基醇和乙二醇的螺硼酸酯5-10，研究了O-苄基肟醚对映选择性硼烷还原为伯胺的过程。在0℃下，仅在二恶烷中使用仅10％的衍生自二苯基缬氨醇的催化剂5实现了有效的催化条件，导致在高达99％的ee下完全转化为相应的伯胺。
• Synthesis of <i>N</i>-alkoxy amines and hydroxylamines <i>via</i> the iridium-catalyzed transfer hydrogenation of oximes
  作者：Yanping Xia、Sen Wang、Rui Miao、Jianhua Liao、Lu Ouyang、Renshi Luo

  DOI：10.1039/d2ob01084d

  日期：——

  hydrogenation of oximes to access N-alkoxy amines and hydroxylamines, and the reaction was accelerated by trifluoroacetic acid. The practical application of this protocol was demonstrated by a gram-scale transformation and two-step synthesis of the fungicide furmecyclox (BAS 389F) in overall yields of 92 and 85%, respectively. An asymmetric protocol using chiral Ir complexes to afford chiral N-alkoxy amines was

  发现阳离子铱（Ir）配合物催化肟的转移加氢以得到N-烷氧基胺和羟胺，并且三氟乙酸加速了反应。该协议的实际应用通过克级转化和杀菌剂 furmecyclox (BAS 389F) 的两步合成得到证明，总产量分别为 92% 和 85%。证明了使用手性 Ir 配合物提供手性N-烷氧基胺的不对称方案，但获得的低产率/ee 表明需要进一步开发。