N-(trans-3,7-dimethyl-2,6-dien-1-yl)-N-methyldiazoacetamide | 175163-95-8

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: N-(trans-3,7-dimethyl-2,6-dien-1-yl)-N-methyldiazoacetamide
• 英文别名: 2-diazo-N-[(2E)-3,7-dimethylocta-2,6-dienyl]-N-methylacetamide
• CAS: 175163-95-8
• 化学式: C₁₃H₂₁N₃O
• 分子量: 235.329
• InChiKey: QAUXCOQSSZHNEF-XYOKQWHBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  17
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.54
• 拓扑面积：
  22.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(trans-3,7-dimethyl-2,6-dien-1-yl)-N-methyldiazoacetamide 在 Rh₂(2(S)-MEOX)4 作用下， 以 二氯甲烷 为溶剂， 反应 10.0h， 生成 1-methyl-4-(6-methyl-5-hepten-2-yl)-1,5-dihydro-2H-pyrrol-2-one 、 (1R,5S,6R)-3,6-Dimethyl-6-(4-methyl-pent-3-enyl)-3-aza-bicyclo[3.1.0]hexan-2-one 、 (1S,5R,6S)-3,6-Dimethyl-6-(4-methyl-pent-3-enyl)-3-aza-bicyclo[3.1.0]hexan-2-one
  参考文献：
  名称：

  Highly Enantioselective Intramolecular Cyclopropanation Reactions of N-Allylic-N-methyldiazoacetamides Catalyzed by Chiral Dirhodium(II) Carboxamidates

  摘要：

  Catalytic diazo decomposition of representative N-allylic-N-methyldiazoacetamides produced the corresponding intramolecular cyclopropanation products in good to excellent yields and with exceptional enantiocontrol. In the simplest case, with N-allyl-N-methyldiazoacetamide, catalysis by dirhodium(II) tetrakis[methyl 2-oxapyrrolidine-5(S)-carboxylate], Rh-2(5(S)-MEPY)(4), achieved the highest yield and enantioselectivity (93% eel. Dirhodium(II) tetrakis[methyl 2-oxo-1-(3-phenylpropanoyl)imidazolidin-4(S)-carboxylate] Rh-2(4S)-MPPIM)(4), was preferred for substituted N-allylic-N-methyldiazoacetamides from which 92-95% ee's were obtained in intramolecular cyclopropanation reactions (88-95% yields), even when the catalyst was employed in only 0.1 mol %, Competition with intramolecular dipolar cycloaddition was minimized with the use of N-methyldiazoacetamides relative to N-tert-butyldiazoacetamides.

  DOI：

  10.1021/jo9519219
• 作为产物：
  描述：

  在 氢氧化钾 、 水 、 三乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 N-(trans-3,7-dimethyl-2,6-dien-1-yl)-N-methyldiazoacetamide
  参考文献：
  名称：

  Highly Enantioselective Intramolecular Cyclopropanation Reactions of N-Allylic-N-methyldiazoacetamides Catalyzed by Chiral Dirhodium(II) Carboxamidates

  摘要：

  Catalytic diazo decomposition of representative N-allylic-N-methyldiazoacetamides produced the corresponding intramolecular cyclopropanation products in good to excellent yields and with exceptional enantiocontrol. In the simplest case, with N-allyl-N-methyldiazoacetamide, catalysis by dirhodium(II) tetrakis[methyl 2-oxapyrrolidine-5(S)-carboxylate], Rh-2(5(S)-MEPY)(4), achieved the highest yield and enantioselectivity (93% eel. Dirhodium(II) tetrakis[methyl 2-oxo-1-(3-phenylpropanoyl)imidazolidin-4(S)-carboxylate] Rh-2(4S)-MPPIM)(4), was preferred for substituted N-allylic-N-methyldiazoacetamides from which 92-95% ee's were obtained in intramolecular cyclopropanation reactions (88-95% yields), even when the catalyst was employed in only 0.1 mol %, Competition with intramolecular dipolar cycloaddition was minimized with the use of N-methyldiazoacetamides relative to N-tert-butyldiazoacetamides.

  DOI：

  10.1021/jo9519219