methyl 2-methyl-3-oxo-1-cyclopentene-1-acetate | 29850-16-6

• 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: methyl 2-methyl-3-oxo-1-cyclopentene-1-acetate
• 英文别名: Methyl 2-(2-methyl-3-oxocyclopenten-1-yl)acetate
• CAS: 29850-16-6
• 化学式: C₉H₁₂O₃
• 分子量: 168.192
• InChiKey: TYXHEVGMNXWACI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.56
• 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 2-methyl-3-oxo-1-cyclopentene-1-acetate 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以92%的产率得到methyl α-diazo-2-methyl-3-oxo-1-cyclopentene-1-acetate
  参考文献：
  名称：

  Stereoselective convergent synthesis of hydroazulenes via an intermolecular cyclopropanation/Cope rearrangement

  摘要：

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethane 1 to a vinylcarbenoid intermediate in the presence of oxygenated dienes led to the direct formation of hydroazulenes 7, 13, and 15-19. The 3 + 4 annulation proceeds by a tandem cyclopropanation/Cope rearrangement sequence. The cyclopropanation is highly stereoselective, favoring the formation of cis-divinylcyclopropanes. Due to the boat transition state required for the Cope rearrangement of cis-divinylcyclopropanes, the hydroazulenes are formed with predictable stereocontrol.

  DOI：

  10.1021/jo00002a044
• 作为产物：
  描述：

  甲基环戊烯醇酮 在 18-冠醚-6 、 potassium tert-butylate 、 calcium carbonate 作用下， 以 xylene 为溶剂， 反应 73.25h， 生成 methyl 2-methyl-3-oxo-1-cyclopentene-1-acetate
  参考文献：
  名称：

  Stereoselective convergent synthesis of hydroazulenes via an intermolecular cyclopropanation/Cope rearrangement

  摘要：

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethane 1 to a vinylcarbenoid intermediate in the presence of oxygenated dienes led to the direct formation of hydroazulenes 7, 13, and 15-19. The 3 + 4 annulation proceeds by a tandem cyclopropanation/Cope rearrangement sequence. The cyclopropanation is highly stereoselective, favoring the formation of cis-divinylcyclopropanes. Due to the boat transition state required for the Cope rearrangement of cis-divinylcyclopropanes, the hydroazulenes are formed with predictable stereocontrol.

  DOI：

  10.1021/jo00002a044

文献信息

• Photochemical Approaches to the Bilobalide Core
  作者：Jens Emsermann、Till Opatz

  DOI：10.1002/ejoc.201700461

  日期：2017.6.23

  Bilobalide is a tetracyclic sesquiterpene containing three contiguous γ-lactone rings and an unusual tert-butyl group, which is found in the leaves of the ginkgo tree (Ginkgo biloba). Three different photochemical approaches towards bilobalide's unique skeleton are presented. A meta photocycloaddition, a [2 + 2] photocycloaddition, and a Paternò–Büchi-reaction were chosen as the respective key steps

  白果内酯是含有三个连续γ内酯环和一个不寻常的四环倍半萜叔丁基，其在银杏树（叶发现银杏）。提出了三种不同的光化学方法对白果内酯独特的骨架。甲元光环，[2 + 2]光环，和一个的Paternò-步琪反应被选为相应关键步骤。
• CIRCULAR ECONOMY METHODS OF PREPARING UNSATURATED COMPOUNDS
  申请人：INTERNATIONAL FLAVORS & FRAGRANCES INC.

  公开号：US20170362155A1

  公开（公告）日：2017-12-21

  Methods of preparing unsaturated compounds or analogs through dehydrogenation of corresponding saturated compounds and/or hydrogenation of aromatic compounds are disclosed.

  通过脱氢饱和化合物和/或芳香化合物氢化的方法制备不饱和化合物或类似物已被披露。
• Davies, Huw M. L.; Huby, Nicholas J. S.; Cantrell Jr., William R., Journal of the American Chemical Society, 1993, vol. 115, # 21, p. 9468 - 9479
  作者：Davies, Huw M. L.、Huby, Nicholas J. S.、Cantrell Jr., William R.、Olive, Jennifer L.

  DOI：——

  日期：——
• CANTRELL, WILLIAM R. (JR);DAVIES, HUW M. L., J. ORG. CHEM., 56,(1991) N, C. 723-727
  作者：CANTRELL, WILLIAM R. (JR)、DAVIES, HUW M. L.

  DOI：——

  日期：——
• Stereoselective convergent synthesis of hydroazulenes via an intermolecular cyclopropanation/Cope rearrangement
  作者：William R. Cantrell、Huw M. L. Davies

  DOI：10.1021/jo00002a044

  日期：1991.1

  Rhodium(II) acetate catalyzed decomposition of vinyldiazomethane 1 to a vinylcarbenoid intermediate in the presence of oxygenated dienes led to the direct formation of hydroazulenes 7, 13, and 15-19. The 3 + 4 annulation proceeds by a tandem cyclopropanation/Cope rearrangement sequence. The cyclopropanation is highly stereoselective, favoring the formation of cis-divinylcyclopropanes. Due to the boat transition state required for the Cope rearrangement of cis-divinylcyclopropanes, the hydroazulenes are formed with predictable stereocontrol.