N-bis(trimethylsilyl)-N-(phenethyl)-α-methoxycarbonyl-α-diazoacetamide | 478369-32-3

• 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)-N-(phenethyl)-α-methoxycarbonyl-α-diazoacetamide
• 英文别名: Methyl 3-[bis(trimethylsilyl)methyl-(2-phenylethyl)amino]-2-diazo-3-oxopropanoate；methyl 3-[bis(trimethylsilyl)methyl-(2-phenylethyl)amino]-2-diazo-3-oxopropanoate
• CAS: 478369-32-3
• 化学式: C₁₉H₃₁N₃O₃Si₂
• 分子量: 405.644
• InChiKey: QZFUSAQBHCXZIL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.02
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  N-bis(trimethylsilyl)-N-(phenethyl)-α-methoxycarbonyl-α-diazoacetamide 在 dirhodium(II) tetrakis 、 sodium chloride 作用下， 以 二氯甲烷 、 水 、 二甲基亚砜 为溶剂， 反应 32.5h， 生成 (R)-4-苯基吡咯烷-2-酮
  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 tetrahydroborate 作用下， 以 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 N-bis(trimethylsilyl)-N-(phenethyl)-α-methoxycarbonyl-α-diazoacetamide
  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

• Asymmetric Intramolecular CH Insertion of α-Diazoacetamides in Water by Dirhodium(II) Catalysts Derived from Natural Amino Acids
  作者：Nuno R. Candeias、Carolina Carias、Luis F. R. Gomes、Vânia André、M. Teresa Duarte、Pedro M. P. Gois、Carlos A. M. Afonso

  DOI：10.1002/adsc.201200101

  日期：2012.11.12

  The asymmetric dirhodium(II)-catalyzed intramolecular CH insertion of α-diazo acetamides in water is described for the first time. The use of natural α-amino acids as chiral ligands allowed the preparation of novel dirhodium(II) homochiral complexes by a simple procedure consisting of the in situ ligand exchange starting from dirhodium tetraacetate. The catalytic system was further reused up to 7 cycles

  首次描述了α-重氮乙酰胺在水中不对称由二碘鎓（II）催化的分子内CH插入。天然α-氨基酸作为手性配体的使用允许通过简单的程序制备新的dirhodium（II）同手性络合物，该程序包括从四乙酸dirhodium开始的原位配体交换。催化体系进一步重复使用多达7个循环，并以良好的收率和过量的对映异构体获得了β-内酰胺。
• Cyclization of Diazoacetamides Catalyzed by N-Heterocyclic Carbene Dirhodium(II) Complexes
  作者：Carlos Afonso、Luis Gomes、Alexandre Trindade、Nuno Candeias、Luís Veiros、Pedro Gois

  DOI：10.1055/s-0029-1217005

  日期：2009.10

  The axial coordination of N-heterocyclic carbene ligands onto dirhodium(II) complexes was examined, together with its role in the intramolecular C-H insertion reactions of α-diazoacetamides. The formation of a decarbonylated product occurs by a free-carbene mechanism in which the structures of the catalyst and the acetamide play a decisive role. carbenoids - carbene complexes - catalysis - diazo compounds

  研究了N-杂环卡宾配体在dirhodium（II）配合物上的轴向配位，及其在α-重氮乙酰胺的分子内CH插入反应中的作用。脱羰基产物的形成是通过游离碳烯机理进行的，其中催化剂和乙酰胺的结构起决定性作用。 类胡萝卜素-卡宾配合物-催化-重氮化合物-铑
• The rhodium(II)-catalyzed reaction of N-bis(trimethylsilylmethyl)diazoamides: steric, electronic and conformational effects
  作者：Andrew G.H Wee、Sammy C Duncan

  DOI：10.1016/s0040-4039(02)01273-x

  日期：2002.8

  insertion reaction occurs only at the other N-‘alkyl’ unit. In Cα-unbranched diazoamides, the inherent electronic effects of the N-‘alkyl’ group influence the regioselectivity of the reaction. The N-BTMSM group also influences the conformational preference about the amide N–Cα bond in Cα-branched systems which, in turn, affects the regioselectivity of the reaction; substituent electronic effects are subtle

  所述Ñ双（三甲基甲硅烷基）甲基（Ñ -BTMSM）基团是有效的关于酰胺NC（O）在叔重氮酯键的构象控制; 金属碳氢化合物C–H插入反应仅在其他N-'烷基'单元发生。在C α -unbranched重氮酯，N型'alkyl”组的固有的电子效应会影响反应的区域选择性。该Ñ -BTMSM基也影响大约酰胺N-C构象偏好α在C键α -支化的系统，进而，影响反应的区域选择性; 取代基的电子效应是微妙的，并起着次要作用。提出了一个过渡状态模型来解释结果。
• 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.