methyl 5-allyl-3,3-dimethyl-6-oxocyclohex-1-enecarboxylate | 1000003-81-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 5-allyl-3,3-dimethyl-6-oxocyclohex-1-enecarboxylate
• 英文别名: Methyl 3,3-dimethyl-6-oxo-5-prop-2-enylcyclohexene-1-carboxylate；methyl 3,3-dimethyl-6-oxo-5-prop-2-enylcyclohexene-1-carboxylate
• CAS: 1000003-81-5
• 化学式: C₁₃H₁₈O₃
• 分子量: 222.284
• InChiKey: LVHFSJYGKLGEQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methyl 5-allyl-3,3-dimethyl-6-oxocyclohex-1-enecarboxylate 在 三氯化铝 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以68%的产率得到methyl 1,8-dimethyl-4-oxobicyclo[3.3.1]non-2-ene-3-carboxylate
  参考文献：
  名称：

  交叉共轭α-烷氧基烯酮体系促进了多烯环化。在路易斯酸催化下观察到假定的1,5-氢化物/ 1,3-烷基转移。

  摘要：

  在AlCl3和/或SnCl4的催化下，化合物3和4的多烯环化反应产生了复杂的双环产物8和9，其结构非常出乎意料，因此需要进行X射线分析以明确进行结构鉴定。从机理上讲，提出了一个串联的sigma键重排过程，其中包括一个不寻常的贯穿空间的1,5-氢化物或1,3-烷基移位作为关键操作。

  DOI：

  10.1021/ol702631q
• 作为产物：
  描述：

  4,4-二甲基-2-羰基甲氧基环己酮 在 potassium carbonate 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 25.0h， 生成 methyl 5-allyl-3,3-dimethyl-6-oxocyclohex-1-enecarboxylate
  参考文献：
  名称：

  Bis-Michael Acceptors as Novel Probes to Study the Keap1/Nrf2/ARE Pathway

  摘要：

  Nuclear factor erythroid 2-related factor 2 (Nrf2) is a master regulator that promotes the transcription of cytoprotective genes in response to oxidative/electrophilic stress. Various Michael-type compounds were designed and synthesized, and their potency to activate the Keap1/Nrf2/ARE pathway was evaluated. Compounds bearing two Michael-type acceptors proved to be the most active. Tether length and rigidity between the acceptors was crucial. This study will help to understand how this feature disrupts the interaction between Keap1 and Nrf2.

  DOI：

  10.1021/acs.jmedchem.6b01132

文献信息

• Polyene Cyclization Promoted by the Cross-Conjugated α-Carbalkoxy Cyclohexenone System. An Unusual 1,2-Hydride Shift under Lewis Acid Catalysis
  作者：Min-Tsang Hsieh、Ho-Hsuan Chou、Hsing-Jang Liu、Huang-Min Wu、Tai Wei Ly、Yen-Ku Wu

  DOI：10.1021/ol802878t

  日期：2009.4.16

  Polyene cyclization of the titled compounds under catalysis with AlCl3/SnCl4 gave rise to the corresponding polycyclic products, many of which were structurally highly unexpected, and thus, individual X-ray analysis was required to finalize the structural identification. Mechanistically, an unusual 1,2-hydride shift is proposed to elucidate the product formation.

  在AlCl 3 / SnCl 4的催化下，标题化合物的多烯环化产生相应的多环产物，其中许多在结构上是高度出乎意料的，因此需要单独的X射线分析来完成结构鉴定。从机理上讲，提出了一种不寻常的1,2-氢化物位移来阐明产物的形成。
• Polyene Cyclization Promoted by the Cross-Conjugated α-Carbalkoxy Enone System. Observation on a Putative 1,5-Hydride/1,3-Alkyl Shift under Lewis Acid Catalysis
  作者：Ho-Hsuan Chou、Huang-Min Wu、Jen-Dar Wu、Tai Wei Ly、Ning-Wei Jan、Kak-Shan Shia、Hsing-Jang Liu

  DOI：10.1021/ol702631q

  日期：2008.1.1

  Polyene cyclization of compounds 3 and 4 under catalysis with AlCl3 and/or SnCl4 gave rise to complex bicyclic products 8 and 9, structures of which were highly unexpected, and X-ray analyses were invoked for unambiguously structural identification. Mechanistically, a tandem sigma-bond rearrangement process, including an unusual through-space 1,5-hydride or 1,3-alkyl shift as a key operation, is proposed

  在AlCl3和/或SnCl4的催化下，化合物3和4的多烯环化反应产生了复杂的双环产物8和9，其结构非常出乎意料，因此需要进行X射线分析以明确进行结构鉴定。从机理上讲，提出了一个串联的sigma键重排过程，其中包括一个不寻常的贯穿空间的1,5-氢化物或1,3-烷基移位作为关键操作。
• Bis-Michael Acceptors as Novel Probes to Study the Keap1/Nrf2/ARE Pathway
  作者：Ludovic J. Deny、Hussein Traboulsi、André M. Cantin、Éric Marsault、Martin V. Richter、Guillaume Bélanger

  DOI：10.1021/acs.jmedchem.6b01132

  日期：2016.10.27

  Nuclear factor erythroid 2-related factor 2 (Nrf2) is a master regulator that promotes the transcription of cytoprotective genes in response to oxidative/electrophilic stress. Various Michael-type compounds were designed and synthesized, and their potency to activate the Keap1/Nrf2/ARE pathway was evaluated. Compounds bearing two Michael-type acceptors proved to be the most active. Tether length and rigidity between the acceptors was crucial. This study will help to understand how this feature disrupts the interaction between Keap1 and Nrf2.