丁酸,2-重氮基-3-羰基-,1,1-二甲基庚基酯 | 127236-71-9

• 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
• 中文名称: 丁酸,2-重氮基-3-羰基-,1,1-二甲基庚基酯
• 英文名称: 2-methyl-2-octyl diazoacetoacetate
• 英文别名: 3-diazonio-4-(2-methyloctan-2-yloxy)-4-oxobut-2-en-2-olate
• CAS: 127236-71-9
• 化学式: C₁₃H₂₂N₂O₃
• 分子量: 254.329
• InChiKey: FBESEAQFADXELM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.54
• 重原子数：
  18.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  79.77
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  丁酸,2-重氮基-3-羰基-,1,1-二甲基庚基酯 在 tetraacetamidatodirhodium(II) 作用下， 生成 2(3H)-呋喃酮,3-乙酰基二氢-5,5-二甲基-4-戊基-,反- 、 3-acetyl-5-n-hexyl-5-methyldihydro-2(3H)-furanone
  参考文献：
  名称：

  在羧酸铑（II）和铑（II）羧酰胺催化的重氮酯的分子内类胡萝卜素碳氢插入中高选择性合成γ-内酯

  摘要：

  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。

  DOI：

  10.1016/s0040-4039(01)93408-2
• 作为产物：
  描述：

  仲辛酮 在 sodium acetate 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 乙腈 为溶剂， 反应 2.0h， 生成 丁酸,2-重氮基-3-羰基-,1,1-二甲基庚基酯
  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