6-(2-Furanyl)-4-(methoxycarbonyl)-3-hexanone | 169892-19-7

• 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: 6-(2-Furanyl)-4-(methoxycarbonyl)-3-hexanone
• 英文别名: Methyl 2-[2-(furan-2-yl)ethyl]-3-oxopentanoate
• CAS: 169892-19-7
• 化学式: C₁₂H₁₆O₄
• 分子量: 224.257
• InChiKey: ZPDZWTOPTYMVQR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  16
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  56.5
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  6-(2-Furanyl)-4-(methoxycarbonyl)-3-hexanone 在 Oxone 、 正丁基锂 、 potassium hydride 、 sodium hydride 、 lithium chloride 作用下， 以 四氢呋喃 、 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 生成 2-<5-Ethoxy-4-ethyl-3-methyl-6-(phenylsulfonyl)-4(E)-hexenyl>furan
  参考文献：
  名称：

  Intramolecular [4+3] Cycloadditions. Studies of Relative Asymmetric Induction

  摘要：

  Treatment df both the E and Z isomers of alkoxyallylic sulfones 20a and 20b with TiCl4 results in the formation of 4 + 3 cycloadducts by intramolecular cycloaddition. The distribution of diastereomers is different from each isomer of educt. This suggests that cycloaddition occurs faster than any isomerization process of the intermediate allylic cations. Both the E and Z isomers of 20c lead to the same 4 + 3 cycloadduct with essentially complete diastereoselectivity. Inherently high simple diastereoselection and a strong conformational bias in the allylic cation intermediates for both isomers account for this selectivity. The importance of allylic cation stereochemistry in these reactions is underscored by the cyclization of 20d. The Z isomer give only 4 + 3 cycloadducts with excellent relative but poor simple diastereoselection, suggestive of a concerted reaction. The E isomer give a [3 + 2] cycloadduct, enol ether 60, as the major cycloadduct as well as 4 + 3 cycloadducts and chloride-trapping product 61. This result is indicative of a stepwise reaction. The data reflect the importance of allylic cation stereochemistry in the regiochemical and stereochemical outcomes of intramolecular 4 + 3 cycloaddition reactions.

  DOI：

  10.1021/jo00121a028
• 作为产物：
  描述：

  β-2-呋喃基乙醇 在 吡啶 、 sodium hydride 、 sodium iodide 作用下， 以 四氢呋喃 、 氯仿 、 丙酮 为溶剂， 反应 67.0h， 生成 6-(2-Furanyl)-4-(methoxycarbonyl)-3-hexanone
  参考文献：
  名称：

  Intramolecular [4+3] Cycloadditions. Studies of Relative Asymmetric Induction

  摘要：

  Treatment df both the E and Z isomers of alkoxyallylic sulfones 20a and 20b with TiCl4 results in the formation of 4 + 3 cycloadducts by intramolecular cycloaddition. The distribution of diastereomers is different from each isomer of educt. This suggests that cycloaddition occurs faster than any isomerization process of the intermediate allylic cations. Both the E and Z isomers of 20c lead to the same 4 + 3 cycloadduct with essentially complete diastereoselectivity. Inherently high simple diastereoselection and a strong conformational bias in the allylic cation intermediates for both isomers account for this selectivity. The importance of allylic cation stereochemistry in these reactions is underscored by the cyclization of 20d. The Z isomer give only 4 + 3 cycloadducts with excellent relative but poor simple diastereoselection, suggestive of a concerted reaction. The E isomer give a [3 + 2] cycloadduct, enol ether 60, as the major cycloadduct as well as 4 + 3 cycloadducts and chloride-trapping product 61. This result is indicative of a stepwise reaction. The data reflect the importance of allylic cation stereochemistry in the regiochemical and stereochemical outcomes of intramolecular 4 + 3 cycloaddition reactions.

  DOI：

  10.1021/jo00121a028

文献信息

• Intramolecular [4+3] Cycloadditions. Studies of Relative Asymmetric Induction
  作者：Michael Harmata、Chandra B. Gamlath、Charles L. Barnes、Darin E. Jones

  DOI：10.1021/jo00121a028

  日期：1995.8

  Treatment df both the E and Z isomers of alkoxyallylic sulfones 20a and 20b with TiCl4 results in the formation of 4 + 3 cycloadducts by intramolecular cycloaddition. The distribution of diastereomers is different from each isomer of educt. This suggests that cycloaddition occurs faster than any isomerization process of the intermediate allylic cations. Both the E and Z isomers of 20c lead to the same 4 + 3 cycloadduct with essentially complete diastereoselectivity. Inherently high simple diastereoselection and a strong conformational bias in the allylic cation intermediates for both isomers account for this selectivity. The importance of allylic cation stereochemistry in these reactions is underscored by the cyclization of 20d. The Z isomer give only 4 + 3 cycloadducts with excellent relative but poor simple diastereoselection, suggestive of a concerted reaction. The E isomer give a [3 + 2] cycloadduct, enol ether 60, as the major cycloadduct as well as 4 + 3 cycloadducts and chloride-trapping product 61. This result is indicative of a stepwise reaction. The data reflect the importance of allylic cation stereochemistry in the regiochemical and stereochemical outcomes of intramolecular 4 + 3 cycloaddition reactions.