(Z)-2-methyl-1-phenylpropan-1-one O-pivaloyl oxime | 1619225-02-3

• 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: (Z)-2-methyl-1-phenylpropan-1-one O-pivaloyl oxime
• 英文别名: [(Z)-(2-methyl-1-phenylpropylidene)amino] 2,2-dimethylpropanoate
• CAS: 1619225-02-3
• 化学式: C₁₅H₂₁NO₂
• 分子量: 247.337
• InChiKey: AGZKBRBGTVZPHN-SSZFMOIBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  38.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  Wilkinson's catalyst 、 (Z)-2-methyl-1-phenylpropan-1-one O-pivaloyl oxime 以 氘代苯 为溶剂， 反应 0.51h， 以39%的产率得到
  参考文献：
  名称：

  肟酯中N–O键的氧化加成引起的C–H活化：Rhodacycles的形成和炔烃的环加成反应

  摘要：

  The reaction of oxime esters with a rhodium(I) precursor to form five-membered rhodacycles via N-O bond cleavage followed by C-H bond activation has been investigated by isolating these complexes. Kinetic studies on the formation of rhodacycles show that the reversible oxidative addition of the N-O bond in the oxime ester to RhCl(PPh3)(3) occurs at room temperature. The E-isomer of the oxime ester was found to undergo rhodacycle formation faster than the Z-isomer, which suggests that the geometry of the oxime esters reflects the geometry of intermediates during C-H activation. The rhodacycle reacted with an alkyne to construct an isoquinoline ring in both stoichiometric and catalytic conditions, despite its basic stability in air, in moisture, and even during heating, which demonstrates the potential of the rhodacycle as an intermediate for further catalytic transformation of oxime esters.

  DOI：

  10.1021/acs.organomet.6b00311
• 作为产物：
  描述：

  异丁酰苯 在 盐酸羟胺 、 potassium acetate 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 1.17h， 生成 (Z)-2-methyl-1-phenylpropan-1-one O-pivaloyl oxime
  参考文献：
  名称：

  甲基酮肟酯作为钯催化的CH烷基化中的亲核性偶合剂，并在异喹啉的合成中应用

  摘要：

  已发现甲基酮肟酯是C（sp 2）–C（sp 3）的极佳偶合伙伴）通过Pd催化的芳族C–H活化形成键。该转化形成了通过与芳基肟酯偶联来区域选择性合成取代的异喹啉的方法的基础。我们的机理研究表明，该反应是通过Pd（II）催化的芳族C–H活化，互变异构以及与Palladacycle连接的甲基酮肟肟酯进行1,3转移而实现的，通过还原消除可形成C–C键。以及亚氨基-Pd（II）中间体的分子内缩合形成杂环。芳基肟基团不仅用作Pd催化的芳族C–H活化的导向基团，而且还用作内部氧化剂，使反应呈氧化还原中性。我们的研究阐明了这种C–H烷基化过程的范围和局限性，

  DOI：

  10.1021/jo5010586

文献信息

• Methyl Ketone Oxime Esters as Nucleophilic Coupling Partners in Pd-Catalyzed C–H Alkylation and Application in the Synthesis of Isoquinolines
  作者：Zhi-Wei Zhang、Aijun Lin、Jiong Yang

  DOI：10.1021/jo5010586

  日期：2014.8.1

  excellent coupling partners for C(sp2)–C(sp3) bond formation via Pd-catalyzed aromatic C–H activation. This transformation forms the basis of an approach to regioselectively synthesize substituted isoquinolines via coupling with aryloxime esters. Our mechanistic studies suggested that the reaction proceeded through Pd(II)-catalyzed aromatic C–H activation, tautomerization, and a 1,3-shift of the palladacycle-ligated

  已发现甲基酮肟酯是C（sp 2）–C（sp 3）的极佳偶合伙伴）通过Pd催化的芳族C–H活化形成键。该转化形成了通过与芳基肟酯偶联来区域选择性合成取代的异喹啉的方法的基础。我们的机理研究表明，该反应是通过Pd（II）催化的芳族C–H活化，互变异构以及与Palladacycle连接的甲基酮肟肟酯进行1,3转移而实现的，通过还原消除可形成C–C键。以及亚氨基-Pd（II）中间体的分子内缩合形成杂环。芳基肟基团不仅用作Pd催化的芳族C–H活化的导向基团，而且还用作内部氧化剂，使反应呈氧化还原中性。我们的研究阐明了这种C–H烷基化过程的范围和局限性，
• C–H Activation Induced by Oxidative Addition of N–O Bonds in Oxime Esters: Formation of Rhodacycles and Cycloaddition with Alkynes
  作者：Takuya Shimbayashi、Kazuhiro Okamoto、Kouichi Ohe

  DOI：10.1021/acs.organomet.6b00311

  日期：2016.6.13

  The reaction of oxime esters with a rhodium(I) precursor to form five-membered rhodacycles via N-O bond cleavage followed by C-H bond activation has been investigated by isolating these complexes. Kinetic studies on the formation of rhodacycles show that the reversible oxidative addition of the N-O bond in the oxime ester to RhCl(PPh3)(3) occurs at room temperature. The E-isomer of the oxime ester was found to undergo rhodacycle formation faster than the Z-isomer, which suggests that the geometry of the oxime esters reflects the geometry of intermediates during C-H activation. The rhodacycle reacted with an alkyne to construct an isoquinoline ring in both stoichiometric and catalytic conditions, despite its basic stability in air, in moisture, and even during heating, which demonstrates the potential of the rhodacycle as an intermediate for further catalytic transformation of oxime esters.