3-allyl-1-benzyl-3-methyl-2-piperidinone | 175912-67-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: 3-allyl-1-benzyl-3-methyl-2-piperidinone
• 英文别名: 3-allyl-1-benzyl-3-methylpiperidin-2-one；1-benzyl-3-methyl-3-prop-2-enylpiperidin-2-one
• CAS: 175912-67-1
• 化学式: C₁₆H₂₁NO
• 分子量: 243.349
• InChiKey: QNFIOOXROPFZMQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  20.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-allyl-1-benzyl-3-methyl-2-piperidinone 在 sodium hydroxide 、 臭氧 作用下， 以 甲醇 为溶剂， 生成 N-benzyl-3-(3'-diazo-2'-oxopropyl)-3-methyl-2-piperidinone
  参考文献：
  名称：

  A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process

  摘要：

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.

  DOI：

  10.1021/jo952078h
• 作为产物：
  描述：

  1-苄基-2-哌啶酮 在 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 1.5h， 生成 3-allyl-1-benzyl-3-methyl-2-piperidinone
  参考文献：
  名称：

  钯（II）催化烯丙基Ç ？H氧化受阻底物的选择性超过氧化程度可调节

  摘要：

  Oxone和钯（II）催化剂的使用可实现位阻α-季内酰胺的有效烯丙基CH氧化，这些胺在已知条件下无法发生类似转化。这种简单，安全，有效的CH活化系统可实现在对烯丙基乙酸酯的双电子氧化与对映体的四电子氧化之间不同寻常的可调节选择性，而主要产物取决于是否存在水。还证明了通过该方法可得到的乙酸烯丙酯和烯醛产品的通用合成效用。

  DOI：

  10.1002/anie.201504007

文献信息

• A Novel Cycloaddition Reaction of α-Diazo-γ-amido Ketones Catalyzed by Rhodium(II) Acetate. Scope and Mechanistic Details of the Process
  作者：Albert Padwa、Alan T. Price、Lin Zhi

  DOI：10.1021/jo952078h

  日期：1996.1.1

  alpha-Diazo ketones containing an amido group in the gamma-position have been found to undergo a novel rhodium(II)-catalyzed cycloaddition reaction. Intramolecular cyclization of the keto carbenoid onto the oxygen atom of the amide group generates a carbonyl ylide dipole as a transient species. This highly stabilized dipole does not readily undergo 1,3-dipolar cycloaddition but rather transfers a proton to produce a cyclic ketene N,O-acetal. The ketene acetal is unstable to moisture and upon standing is readily hydrolyzed to a gamma-keto delta-lactone and an amine. In the absence of any significant amount of water, the ketene N,O-acetal undergoes conjugate addition with the activated st-bond of the dipolarophile to give a zwitterion intermediate. The anionic portion of the zwitterion adds to the neighboring carbonyl group. This is followed by epoxide ring formation with charge dissipation leading to an amido-substituted spiro cyclopentyl epoxide. In certain cases a hydroxy lactone was also isolated and its formation can be attributed to the competitive hydrolysis of the zwitterionic intermediate. The Rh(II)-catalyzed reaction of the diazo ketoamide derived from N-benzylpiperidone with DMAD afforded two different types of cycloadducts. In addition to the spiro cyclopentyl epoxide, a product derived from trapping of the carbonyl ylide dipole was also obtained, thereby providing additional support for the proposed mechanism.
• Palladium(II)-Catalyzed Allylic CH Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation
  作者：Xiangyou Xing、Nicholas R. O'Connor、Brian M. Stoltz

  DOI：10.1002/anie.201504007

  日期：2015.9.14

  use of Oxone and a palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered α‐quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for CH activation allows for unusual tunable selectivity between a two‐electron oxidation to the allylic acetates and a four‐electron oxidation to the corresponding

  Oxone和钯（II）催化剂的使用可实现位阻α-季内酰胺的有效烯丙基CH氧化，这些胺在已知条件下无法发生类似转化。这种简单，安全，有效的CH活化系统可实现在对烯丙基乙酸酯的双电子氧化与对映体的四电子氧化之间不同寻常的可调节选择性，而主要产物取决于是否存在水。还证明了通过该方法可得到的乙酸烯丙酯和烯醛产品的通用合成效用。