1-(ethoxycarbonyl)-2-(octylidene)cyclopropylmethyl ketone

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: 1-(ethoxycarbonyl)-2-(octylidene)cyclopropylmethyl ketone
• 英文别名: 1-ethoxycarbonyl-2-(octylidene)cyclopropyl methyl ketone；Ethyl 1-acetyl-2-octylidenecyclopropane-1-carboxylate；ethyl 1-acetyl-2-octylidenecyclopropane-1-carboxylate
• 化学式: C₁₆H₂₆O₃
• 分子量: 266.381
• InChiKey: AQOOBBQWOYRENT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  1-(ethoxycarbonyl)-2-(octylidene)cyclopropylmethyl ketone 在 sodium iodide 作用下， 以 丙酮 为溶剂， 反应 24.0h， 以75%的产率得到2-methyl-3-ethoxycarbonyl-4-(n-octyl)furan
  参考文献：
  名称：

  亚甲基或亚烷基环丙基酮开环环异构化反应的催化区域选择性控制

  摘要：

  2-亚甲基-或亚烷基环丙烷基酮很容易通过丙二烯的区域选择性环丙烷化反应或亚甲基-/亚烷基环丙烷基锂与N,N-二甲基羧酸酰胺的反应来制备。由于外环 C=C 键和应变环丙烷的存在，它们使用 PdCl(2)(CH(3)CN)(2)、NaI（或 PdCl(2)(CH (3)CN)(2) + NaI) 和 Pd(PPh(3))(4) 作为催化剂提供了五种不同的产物，即 4H-吡喃、2,3,4-三取代呋喃（或 4,5-二取代-3-亚烷基-2,3-二氢呋喃）和2,3,4,5-四取代呋喃（或2,4,5-三取代-3-亚烷基-2,3-二氢呋喃）分别以良好的产率，取决于催化剂的性质和反应条件。这些产物中较少取代的 C=C 键可以被高度选择性地氢化或硼氢化以​​立体选择性地提供新的杂环产物。这三种类型的不同反应可能通过环丙烷环中碳-碳单键的高度区域选择性裂解进行，由 C=C 键的区域选择性卤金属化和β-脱碳钯化，

  DOI：

  10.1021/ja0494860

文献信息

• Studies on the factors controlling the stereoselectivity in electrophilic iodocyclization of alkylidenecyclopropyl ketones
  作者：Jie Chen、Lianghua Lu、Shengming Ma

  DOI：10.1016/j.tet.2008.06.060

  日期：2008.9

  An efficient electrophilic iodocyclization of alkylidenecyclopropyl ketones with N-iodosuccinimide (NIS) or l(2) in aqueous CH3CN affording 3-oxabicyclo[3.1.0]hexan-2-ols is described. NIS is a better electrophilic iodocyclization reagent than l(2). Four chiral centers were formed within one step. The stereochemistry was established by the X-ray diffraction studies of compounds 2e-2h, 2n, and 2c. It is quite interesting to observe that the substituent of the cyclopropane ring plays an important role in determining the relative stereochemistry at the 4-position: with R-2 being an acyl or ester group a mixture of (1S*,2R*,4S*5R*)-2 (major) and (1R*,2R*,4R*,5R*)-2 (minor) was formed with moderate selectivity while the reaction of the substrates with R being sulfonyl and p-methylphenylsulfonyl or R-1 being phenyl afforded (1R*,2R*,4S*,5S*)-2 or (1S*,2R*,4S*,5R*)-2f as the only product. The reaction is general for a range of different substrates to afford the products in moderate to high yields. (C) 2008 Elsevier Ltd. All rights reserved.
• Preparation of 1-Benzyl-2-methyl-3-(ethoxycarbonyl)-4- (2-phenylethyl)-1H-pyrrole from 4-Phenyl-1,2-butadiene
  作者：Ni, Shengjun、Zhu, Can、Chen, Jie、Ma, Shengming

  DOI：10.15227/orgsyn.090.0327

  日期：——

  Caution! Ethyl alpha-diazoacetoacetate is a potentially explosive material. Transformations involving this compound should be performed behind a blast shield in a well-ventilated fume hood.
• Tuning the Regioselectivity in the Palladium(II)-Catalyzed Isomerization of Alkylidene Cyclopropyl Ketones: A Dramatic Salt Effect
  作者：Shengming Ma、Junliang Zhang

  DOI：10.1002/anie.200390073

  日期：2003.1.13
• Ring-Opening Cyclization of Alkylidenecyclopropyl Ketones with Amines. An Efficient Synthesis of 2,3,4-Trisubstituted Pyrroles
  作者：Lianghua Lu、Guofei Chen、Shengming Ma

  DOI：10.1021/ol052797a

  日期：2006.3.2

  An efficient synthesis of 2,3,4-trisubstituted pyrroles via intermolecular cyclization of alkylidenecyclopropyl ketones with amines was observed. The addition of anhydrous MgSO4 improved the yields of the products 3. A possible mechanism involving the distal cleavage of the C-C bond of cyclopropane ring was proposed.
• Catalytic Regioselectivity Control in Ring-Opening Cycloisomerization of Methylene- or Alkylidenecyclopropyl Ketones
  作者：Shengming Ma、Lianghua Lu、Junliang Zhang

  DOI：10.1021/ja0494860

  日期：2004.8.1

  hydrogenated or hydroborated to afford new heterocyclic products stereoselectively. These three types of different reactions may proceed through a highly regioselective cleavage of a carbon-carbon single bond in the cyclopropane ring triggered by regioselective halometalation of the C=C bond and beta-decarbopalladation, halogen anion attack on the nonsubstituted carbon atom of the cyclopropane ring, or

  2-亚甲基-或亚烷基环丙烷基酮很容易通过丙二烯的区域选择性环丙烷化反应或亚甲基-/亚烷基环丙烷基锂与N,N-二甲基羧酸酰胺的反应来制备。由于外环 C=C 键和应变环丙烷的存在，它们使用 PdCl(2)(CH(3)CN)(2)、NaI（或 PdCl(2)(CH (3)CN)(2) + NaI) 和 Pd(PPh(3))(4) 作为催化剂提供了五种不同的产物，即 4H-吡喃、2,3,4-三取代呋喃（或 4,5-二取代-3-亚烷基-2,3-二氢呋喃）和2,3,4,5-四取代呋喃（或2,4,5-三取代-3-亚烷基-2,3-二氢呋喃）分别以良好的产率，取决于催化剂的性质和反应条件。这些产物中较少取代的 C=C 键可以被高度选择性地氢化或硼氢化以​​立体选择性地提供新的杂环产物。这三种类型的不同反应可能通过环丙烷环中碳-碳单键的高度区域选择性裂解进行，由 C=C 键的区域选择性卤金属化和β-脱碳钯化，