2endo,4endo-2,4-dimethyl-8-methoxycarbonyl-8-azabicyclo[3.2.1]oct-6-en-3-one | 53406-52-3

• 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: 2endo,4endo-2,4-dimethyl-8-methoxycarbonyl-8-azabicyclo[3.2.1]oct-6-en-3-one
• 英文别名: methyl 2α,4α-dimethyl-3-oxo-8-azabicyclo<3.2.1>oct-6-ene-8-carboxylate；methyl 2α,4α-dimethyl-3-oxo-8-azabicyclo[3.2.1]oct-6-ene-8-carboxylate；cis-endo-2,4-dimethyl-8-methoxycarbonyl-8-azabicyclo[3.2.1]oct-6-en-3-one；methyl (1S,2R,4S,5R)-2,4-dimethyl-3-oxo-8-azabicyclo[3.2.1]oct-6-ene-8-carboxylate
• CAS: 53406-52-3
• 化学式: C₁₁H₁₅NO₃
• 分子量: 209.245
• InChiKey: HCNATPBJQHLMJJ-OJOKCITNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  46.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2endo,4endo-2,4-dimethyl-8-methoxycarbonyl-8-azabicyclo[3.2.1]oct-6-en-3-one 在 草酰氯 、 二甲基亚砜 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 2.67h， 生成 methyl 2β-benzoyl-2α,4α-dimethyl-3-oxo-8-azabicyclo[3.2.1]oct-6-ene-8-carboxylate
  参考文献：
  名称：

  Synthesis and Functionalization of New Tropanes Designed for Use as Scaffolds in Combinatorial Chemistry

  摘要：

  DOI：

  10.1002/1099-0690(200012)2000:23<3909::aid-ejoc3909>3.0.co;2-r
• 作为产物：
  描述：

  甲基吡咯-1-羧酸酯 、 2,4-二溴-3-戊酮 在 diethylzinc 作用下， 以 正己烷 、 苯 为溶剂， 以55%的产率得到2endo,4endo-2,4-dimethyl-8-methoxycarbonyl-8-azabicyclo[3.2.1]oct-6-en-3-one
  参考文献：
  名称：

  Mann, John; Barbosa, Luiz-Claudio de Almeida, Journal of the Chemical Society. Perkin transactions I, 1992, # 7, p. 787 - 790

  摘要：

  DOI：

文献信息

• New methodology for the [4+3] cycloaddition reactions: generation of oxyallyl cations from α,α′-diiodoketones under sonochemical or thermal conditions
  作者：Angel M Montaña、Pedro M Grima

  DOI：10.1016/s0040-4039(01)01671-9

  日期：2001.10

  A new methodology to perform [4+3] cycloaddition reactions of suitable dienes and 1,3-dimethyl-2-oxyallyl cations is presented. The reaction is carried out starting from commercially available dienes and easy-handling α,α′-diiodoketones, which are reduced by the Zn/Cu couple to generate the oxyallyl cation as intermediate. The reaction is carried out under mild thermal or sonochemical conditions at

  提出了一种进行合适的二烯与1,3-二甲基-2-氧基烯丙基阳离子的[4 + 3]环加成反应的新方法。该反应从可商购获得的二烯和易于处理的α，α′-二碘酮开始进行，所述α，α′-二碘酮通过Zn / Cu对被还原以产生作为中间体的羟基烯丙基阳离子。该反应在温和的热或声化学条件下于低温（0至-44°C）下进行，反应时间短（<15分钟）。该方法学代表了基于其他还原剂或从更复杂的羟烯丙基阳离子前体开始的实际程序的良好替代性方面。
• Facile Synthesis and Ring-Opening Cross Metathesis of Carbo- and Heterocyclic Bicyclo[3.2.1]oct-6-en-3-ones Using Gaseous Olefinic Reaction Partners
  作者：Marko D. Mihovilovic、Birgit Grötzl、Wolfgang Kandioller、Radka Snajdrova、Adél Muskotál、Dario A. Bianchi、Peter Stanetty

  DOI：10.1002/adsc.200505375

  日期：2006.3

  were prepared by a facile [4+3]-cycloaddition strategy involving sonochemistry. The oxyallyl species required for the reaction with the corresponding diene was generated from a suitable perbromo ketone with activated zinc under sonification conditions. The resulting dibromo bicyclo compounds were reduced to the target products using a Cu/Zn couple. Ring-opening cross metathesis of the resulting bicyclic

  通过涉及声化学的简便的[4 + 3]-环加成策略制备标题化合物。与合适的二烯反应所需的羟基烯丙基物质是在超声条件下由合适的具有活化锌的全溴酮生成的。使用Cu / Zn对将所得的二溴双环化合物还原为目标产物。建立了所得双环物质的开环交叉复分解反应，作为非对映选择性制备顺-3,5-二取代环酮的有效方法。尤其是气态烯烃会给出对称和不对称的产物，作为后续转化的通用平台。这是非应变环系统的这种开环反应的第一个例子。
• Generation of Oxyallyl Cations by Reduction of α,α′-Diiodoketones Under Sonochemical or Thermal Conditions: Improved Methodology for the [4C(4π;)+3C(2π;)] Cycloaddition Reactions
  作者：Angel M. Montaña、Pedro M. Grima

  DOI：10.1081/scc-120015712

  日期：2003.3

  An improved methodology to carry out [4C(4pi)+3C(2pi)] cycloaddition reactions of dienes and oxyallyl cations, is presented. The reaction starts from commercially available dienes and easy-handling alpha,alpha-diio-doketones, which are reduced by Zn (powder) or Zn/Cu couple to generate an oxyallyl cation as an intermediate. The reaction is carried out under mild thermal or sonochemical conditions at low tempera tures (from 0 to -44degreesC) and for short reaction times (< 15 min).