3-acetyl-5-n-hexyl-5-methyldihydro-2(3H)-furanone | 127236-72-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 3-acetyl-5-n-hexyl-5-methyldihydro-2(3H)-furanone
• 英文别名: 3-acetyl-5-hexyl-5-methyloxolan-2-one
• CAS: 127236-72-0
• 化学式: C₁₃H₂₂O₃
• 分子量: 226.316
• InChiKey: QZHPHZZKQNLCFL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  16.0
• 可旋转键数：
  6.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  仲辛酮 在 dirhodium(II) pentafluorobutyrate (Rh₂(pfb)4) sodium acetate 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 、 苯 为溶剂， 反应 2.0h， 生成 3-acetyl-5-n-hexyl-5-methyldihydro-2(3H)-furanone
  参考文献：
  名称：

  Electronic and steric control in carbon-hydrogen insertion reactions of diazoacetoacetates catalyzed by dirhodium(II) carboxylates and carboxamides

  摘要：

  Carboxylate and carboxamide ligands on dirhodium(II) catalysts can provide enormous regiocontrol in carbon-hydrogen insertion reactions of diazoacetate esters. Whereas 2,3,4-trimethyl-3-pentyl diazoacetoacetate (1) forms gamma-lactone products from insertion into primary and tertiary C-H bonds in a statistical distribution (61:39) with dirhodium(II) tetrakis(perfluorobutyrate), only tertiary C-H insertion is observed with dirhodium(II) tetraacetamide. Similar results are obtained with 2-methyl-2-octyl diazoacetoacetate (3), where competition for insertion exists between secondary and primary C-H bonds and electronic factors govern regioselection. However, with 2-methyl-3-isopropyl-3-heptyl diazoacetoacetate (2) and 2-methyl-1-phenyl-2-propyl diazoacetoacetate (4), product distributions from C-H insertion are invariant with the dirhodium(II) ligands; insertion into a secondary C-H bond is favored over tertiary C-H insertion with 2 (95:5), and insertion into a primary C-H bond is preferred to benzylic secondary C-H insertion with 4 (70:30). In such cases, which are amenable to analyses by MM2 calculations, regioselectivity is determined by conformational preferences for which C-H insertion selectivity can be as random as that found with 2 and 4. When only one C-H bond site is available for insertion to form a five-membered ring product, only one gamma-lactone is observed from reactions catalyzed by dirhodium(II) tetraacetate, and that product is not necessarily the one predicted by presumed electronic preferences.

  DOI：

  10.1021/ja00056a021

文献信息

• Highly selective γ-lactone syntheses by intramolecular carbenoid carbon-hydrogen insertion in rhodium(II) carboxylate and rhodium(II) carboxamide catalyzed reactions of diazo esters
  作者：Michael P. Doyle、Vahid Bagheri、Matthew M. Pearson、John D. Edwards

  DOI：10.1016/s0040-4039(01)93408-2

  日期：——

  Rhodium(II) acetate and rhodium(II) acetamide catalyzed decomposition of diazo esters forms γ-lactones in high yield and with exceptionally high regio- and diastereoselectivity.

  乙酸铑（II）和铑（II）乙酰胺催化的重氮酯分解形成γ-内酯，产率高，区域选择性和非对映选择性高。