N-bis(trimethylsilyl)methyl-N-[2-(4-methoxyphenyl)ethyl]-α-methoxycarbonyl-α-diazoacetamide | 882408-54-0

• 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
• 英文名称: N-bis(trimethylsilyl)methyl-N-[2-(4-methoxyphenyl)ethyl]-α-methoxycarbonyl-α-diazoacetamide
• 英文别名: Methyl 3-[bis(trimethylsilyl)methyl-[2-(4-methoxyphenyl)ethyl]amino]-2-diazo-3-oxopropanoate；methyl 3-[bis(trimethylsilyl)methyl-[2-(4-methoxyphenyl)ethyl]amino]-2-diazo-3-oxopropanoate
• CAS: 882408-54-0
• 化学式: C₂₀H₃₃N₃O₄Si₂
• 分子量: 435.671
• InChiKey: LHGUKBMHXTYBSB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.03
• 重原子数：
  29
• 可旋转键数：
  10
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  57.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-bis(trimethylsilyl)methyl-N-[2-(4-methoxyphenyl)ethyl]-α-methoxycarbonyl-α-diazoacetamide 在 dirhodium(II) tetrakis[(S)-N-phthaloyl-tert-leucinate] 、 sodium chloride 作用下， 以 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 19.0h， 生成 1-methyl-4-(4-methoxyphenyl)-2-pyrrolidinone
  参考文献：
  名称：

  Intramolecular asymmetric C–H insertion of N-arylalkyl, N-bis(trimethylsilyl)methyldiazoamides mediated by chiral rhodium(II) catalysts. Synthesis of (R)-β-benzyl-γ-aminobutyric acid

  摘要：

  The enantio- and site-selectivity of the intramolecular C-H insertion reactions of acyclic N-arylalkyl, N-bis(trimethylsilyl)methyl alpha-diazoacetamides, and alpha-carboalkoxy-alpha-diazoacetamides 1a-g, catalyzed by chiral Rh(II) carboxamidates and Rh(II) carboxylates were studied. In general, the reaction showed good to excellent chemoselectivity. Regio selectivity for most of the reactions was high, but was also found to be influenced by the structure of the diazo substrate and the chiral Rh(II) catalyst employed. The highest enantioselectivity for the reactions catalyzed by chiral Rh(II) carboxamidates was 69% and Rh-2(4R-MEOX)(4) was found to be the most effective. For the chiral Rh(II) carboxylate catalyzed reactions, the highest ee obtained was 75% and Rh-2(S-PTTL)(4) is the optimal catalyst. The method was applied toward the synthesis of a GABA analogue, (R)-beta-benzyl-gamma-aminobutyric acid. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.12.020
• 作为产物：
  描述：

  二(三甲基硅基)甲胺 在 2,6-二甲基吡啶 、 sodium carbonate 、 sodium iodide 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.0h， 生成 N-bis(trimethylsilyl)methyl-N-[2-(4-methoxyphenyl)ethyl]-α-methoxycarbonyl-α-diazoacetamide
  参考文献：
  名称：

  Intramolecular asymmetric C–H insertion of N-arylalkyl, N-bis(trimethylsilyl)methyldiazoamides mediated by chiral rhodium(II) catalysts. Synthesis of (R)-β-benzyl-γ-aminobutyric acid

  摘要：

  The enantio- and site-selectivity of the intramolecular C-H insertion reactions of acyclic N-arylalkyl, N-bis(trimethylsilyl)methyl alpha-diazoacetamides, and alpha-carboalkoxy-alpha-diazoacetamides 1a-g, catalyzed by chiral Rh(II) carboxamidates and Rh(II) carboxylates were studied. In general, the reaction showed good to excellent chemoselectivity. Regio selectivity for most of the reactions was high, but was also found to be influenced by the structure of the diazo substrate and the chiral Rh(II) catalyst employed. The highest enantioselectivity for the reactions catalyzed by chiral Rh(II) carboxamidates was 69% and Rh-2(4R-MEOX)(4) was found to be the most effective. For the chiral Rh(II) carboxylate catalyzed reactions, the highest ee obtained was 75% and Rh-2(S-PTTL)(4) is the optimal catalyst. The method was applied toward the synthesis of a GABA analogue, (R)-beta-benzyl-gamma-aminobutyric acid. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2005.12.020