ethyl 2-methyl-1-methylene-1,2,3,4-tetrahydronaphthalene-2-carboxylate | 1203476-56-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: ethyl 2-methyl-1-methylene-1,2,3,4-tetrahydronaphthalene-2-carboxylate
• 英文别名: Ethyl 2-methyl-1-methylidene-3,4-dihydronaphthalene-2-carboxylate
• CAS: 1203476-56-5
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: RZJYBPVPLLBUEJ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 2-methyl-1-methylene-1,2,3,4-tetrahydronaphthalene-2-carboxylate 在 吡啶 、 aluminum (III) chloride 、 lithium aluminium tetrahydride 、 2,4,5,6-四(9H-咔唑-9-基)异酞腈 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 0.7h， 生成 4-(1a-methyl-1a,2,3,7b-tetrahydro-1H-cyclopropa[a]naphthalen-7b-yl)butyl benzoate
  参考文献：
  名称：

  自由基-极性交叉环结：访问多环环丙烷的平台

  摘要：

  光氧化还原介导的自由基/极性交叉（RPC）工艺提供了具有挑战性的环空解决方案。在本文中，我们描述了一种嵌入双环支架内的烯烃的环丙烷化方法。众所周知，这些系统对经典的环丙烷化方法难以抗拒，而RPC环丙烷化可以轻松实施，从而形成多碳环和多杂环环丙烷。环丙烷化的过程是通过添加光致氧化还原的Giese型自由基进行的，然后在新戊基离去基团上进行分子内阴离子取代反应。

  DOI：

  10.1002/adsc.201901051
• 作为产物：
  描述：

  3,4-二氢-1(2H)-萘酮 在 potassium tert-butylate 、 sodium hydride 、 potassium carbonate 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 49.17h， 生成 ethyl 2-methyl-1-methylene-1,2,3,4-tetrahydronaphthalene-2-carboxylate
  参考文献：
  名称：

  自由基-极性交叉环结：访问多环环丙烷的平台

  摘要：

  光氧化还原介导的自由基/极性交叉（RPC）工艺提供了具有挑战性的环空解决方案。在本文中，我们描述了一种嵌入双环支架内的烯烃的环丙烷化方法。众所周知，这些系统对经典的环丙烷化方法难以抗拒，而RPC环丙烷化可以轻松实施，从而形成多碳环和多杂环环丙烷。环丙烷化的过程是通过添加光致氧化还原的Giese型自由基进行的，然后在新戊基离去基团上进行分子内阴离子取代反应。

  DOI：

  10.1002/adsc.201901051

文献信息

• Cyclization of Arylacetoacetates to Indene and Dihydronaphthalene Derivatives in Strong Acids. Evidence for Involvement of Further Protonation of O,O-Diprotonated β-Ketoester, Leading to Enhancement of Cyclization
  作者：Hiroaki Kurouchi、Hiromichi Sugimoto、Yuko Otani、Tomohiko Ohwada

  DOI：10.1021/ja908749u

  日期：2010.1.20

  The chemical features, such as substrate stability, product distribution, and substrate generality, and the reaction mechanism of Bronsted superacid-catalyzed cyclization reactions of aromatic ring-containing acetoacetates (beta-ketoesters) were examined in detail. While two types of carbonyl cyclization are possible, i.e., keto cyclization and ester cyclization, the former was found to take place exclusively. The reaction constitutes an efficient method to synthesize indene and 3,4-dihydronapthalene derivatives. Acid-base titration monitored with C-13 NMR spectroscopy showed that the acetoacetates are fully O-1,O-3-diprotonated at H-0 = -11. While the five-membered ring cyclization of the arylacetoacetates proceeded slowly at H-0 = -11, a linear increase in the rate of the cyclization was found with increasing acidity in the high acidity region of H-0 = -11.8 to -13.3. Therefore, the O-1,O-3-diprotonated acetoacetates exhibited some cyclizing reactivity, but they are not the reactive intermediates responsible for the acceleration of the cyclization in the high acidity region. The reactive cationic species might be formed by further protonation (or protosolvation) of the O-1,O-3-diprotonated acetoacetates; i.e., they may be tricationic species. Thermochemical data on the acid-catalyzed cyclization of the arylacetoacetates showed that the activation energy is decreased significantly as compared with that of the related acid-catalyzed cyclization reaction of a compound bearing a single functional group, such as a ketone. These findings indicate that intervention of the trication contributes to the activation of the cyclization of arylacetoacetates in strong acid, and the electron-withdrawing nature of the O-protonated ester functionality significantly increases the electrophilicity of the ketone moiety.