(E)-2-methylenecycloheptanone O-pivaloyl oxime | 1561177-15-8

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: (E)-2-methylenecycloheptanone O-pivaloyl oxime
• CAS: 1561177-15-8
• 化学式: C₁₃H₂₁NO₂
• 分子量: 223.315
• InChiKey: XILODOJLZHYWAQ-SDNWHVSQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.45
• 重原子数：
  16.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  38.66
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-甲基-4-戊烯酸乙酯 、 (E)-2-methylenecycloheptanone O-pivaloyl oxime 在 六氟异丙醇 、 [Cp*^CF3Rh(MeCN)₃](SbF₆)₂ 、 cesium acetate 作用下， 反应 12.0h， 以85%的产率得到(R)-ethyl 3-(3-methyl-3,5,6,7,8,9-hexahydro-2H-cycloheptapyridin-3-yl)propanoate
  参考文献：
  名称：

  Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C–H Activation

  摘要：

  alpha,beta-Unsaturated - oxime pivalates are proposed to undergo reversible C(sp(2))-H insertion with cationic Rh (III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to. convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.

  DOI：

  10.1021/jacs.5b04946
• 作为产物：
  描述：

  环庚酮 在 吗啉 、 盐酸羟胺 、 sodium carbonate 、 溶剂黄146 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 38.0h， 生成 (E)-2-methylenecycloheptanone O-pivaloyl oxime
  参考文献：
  名称：

  Expedient Access to 2,3-Dihydropyridines from Unsaturated Oximes by Rh(III)-Catalyzed C–H Activation

  摘要：

  alpha,beta-Unsaturated - oxime pivalates are proposed to undergo reversible C(sp(2))-H insertion with cationic Rh (III) complexes to furnish five-membered metallacycles. In the presence of 1,1-disubstituted olefins, these species participate in irreversible migratory insertion to give, after reductive elimination, 2,3-dihydropyridine products in good yields. Catalytic hydrogenation can then be used to. convert these molecules into piperidines, which are important structural components of numerous pharmaceuticals.

  DOI：

  10.1021/jacs.5b04946

文献信息

• Rh(III)-Catalyzed Decarboxylative Coupling of Acrylic Acids with Unsaturated Oxime Esters: Carboxylic Acids Serve as Traceless Activators
  作者：Jamie M. Neely、Tomislav Rovis

  DOI：10.1021/ja412444d

  日期：2014.2.19

  α,β-Unsaturated carboxylic acids undergo Rh(III)-catalyzed decarboxylative coupling with α,β-unsaturated O-pivaloyl oximes to provide substituted pyridines in good yield. The carboxylic acid, which is removed by decarboxylation, serves as a traceless activating group, giving 5-substituted pyridines with very high levels of regioselectivity. Mechanistic studies rule out a picolinic acid intermediate

  α,β-不饱和羧酸与α,β-不饱和O-新戊酰基肟进行Rh(III)催化的脱羧偶联，以良好的收率提供取代的吡啶。通过脱羧去除的羧酸作为无痕活化基团，产生具有非常高区域选择性的 5-取代吡啶。机理研究排除了吡啶甲酸中间体，可分离的铑配合物进一步阐明了反应机理。