2,2-Dimethyl-1,3-dioxolane-4(S)-methyl diazoacetate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-Dimethyl-1,3-dioxolane-4(S)-methyl diazoacetate
• 英文别名: [(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]methyl 2-diazoacetate
• 化学式: C₈H₁₂N₂O₄
• 分子量: 200.194
• InChiKey: GSLNKZGGVBLVKW-ZCFIWIBFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-1,3-dioxolane-4(S)-methyl diazoacetate 在 dirhodium(II) tetrakis(caprolactam) 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到(S)-7,7-Dimethyl-2,6,8-trioxaspiro<4.4>nonan-3-one
  参考文献：
  名称：

  Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

  摘要：

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.

  DOI：

  10.1021/jo00115a018
• 作为产物：
  描述：

  在 lithium hydroxide 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 生成 2,2-Dimethyl-1,3-dioxolane-4(S)-methyl diazoacetate
  参考文献：
  名称：

  Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

  摘要：

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.

  DOI：

  10.1021/jo00115a018