Methyl 3-[bis(trimethylsilyl)methyl-(3-phenylpropyl)amino]-2-diazo-3-oxopropanoate | 866807-65-0

• 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: Methyl 3-[bis(trimethylsilyl)methyl-(3-phenylpropyl)amino]-2-diazo-3-oxopropanoate
• 英文别名: methyl 3-[bis(trimethylsilyl)methyl-(3-phenylpropyl)amino]-2-diazo-3-oxopropanoate
• CAS: 866807-65-0
• 化学式: C₂₀H₃₃N₃O₃Si₂
• 分子量: 419.671
• InChiKey: LRFHQZWBYIXRFR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.42
• 重原子数：
  28
• 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：
  48.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 3-[bis(trimethylsilyl)methyl-(3-phenylpropyl)amino]-2-diazo-3-oxopropanoate 在 dirhodium(II) tetrakis 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到1-bis(trimethylsilyl)methyl-3-methoxycarbonyl-4-benzyl-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 Methyl 3-[bis(trimethylsilyl)methyl-(3-phenylpropyl)amino]-2-diazo-3-oxopropanoate
  参考文献：
  名称：

  双（三甲基甲硅烷基）甲基作为重氮（II）催化的重氮酰胺反应中的有效N保护基和位点选择控制元素。

  摘要：

  研究了分子内铑（II）-类胡萝卜素介导的结构变化的N-双（三甲基甲硅烷基）甲基，N-取代的重氮酰胺的CH插入反应。已经发现在叔重氮酰胺中，N-双（三甲基甲硅烷基）甲基（N- BTMSM）基团可有效控制酰胺N-C（O）键的构象。CH插入发生在另一个N取代基上。在C α -支化的重氮酯，所述Ñ -BTMSM被发现也施加关于所述N-C构象偏好其影响α键，影响在这些系统中CH插入的区域选择性。在直链重氮酰胺中，N取代基的固有电子效应会影响反应的区域选择性和化学选择性。但是，在支链重氮酰胺中，类胡萝卜素碳上的N-取代基和α-取代基的电子效应微妙，但在决定反应的最终结果中很重要。

  DOI：

  10.1021/jo051042e

文献信息

• The Bis(trimethylsilyl)methyl Group as an Effective N-Protecting Group and Site-Selective Control Element in Rhodium(II)-Catalyzed Reaction of Diazoamides
  作者：Andrew G. H. Wee、Sammy C. Duncan

  DOI：10.1021/jo051042e

  日期：2005.10.1

  varied N-bis(trimethylsilyl)methyl,N-substituted diazoamides is studied. It has been found that in tertiary diazoamides the N-bis(trimethylsilyl)methyl (N-BTMSM) group is effective for conformational control about the amide N−C(O) bond; C−H insertion occurs at the other N-substituent. In Cα-branched diazoamides, the N-BTMSM is found also to exert its influence on the conformational preference about the

  研究了分子内铑（II）-类胡萝卜素介导的结构变化的N-双（三甲基甲硅烷基）甲基，N-取代的重氮酰胺的CH插入反应。已经发现在叔重氮酰胺中，N-双（三甲基甲硅烷基）甲基（N- BTMSM）基团可有效控制酰胺N-C（O）键的构象。CH插入发生在另一个N取代基上。在C α -支化的重氮酯，所述Ñ -BTMSM被发现也施加关于所述N-C构象偏好其影响α键，影响在这些系统中CH插入的区域选择性。在直链重氮酰胺中，N取代基的固有电子效应会影响反应的区域选择性和化学选择性。但是，在支链重氮酰胺中，类胡萝卜素碳上的N-取代基和α-取代基的电子效应微妙，但在决定反应的最终结果中很重要。
• 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
  作者：Andrew G.H. Wee、Sammy C. Duncan、Gao-jun Fan

  DOI：10.1016/j.tetasy.2005.12.020

  日期：2006.1

  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.