Methyl 2-formamido-2-(trimethylsiloxy)propanoate | 109053-95-4

• 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 2-formamido-2-(trimethylsiloxy)propanoate
• 英文别名: Methyl 2-formamido-2-trimethylsilyloxypropanoate
• CAS: 109053-95-4
• 化学式: C₈H₁₇NO₄Si
• 分子量: 219.313
• InChiKey: LQWJBWPYNGKOER-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.47
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Methyl 2-formamido-2-(trimethylsiloxy)propanoate 在 palladium on activated charcoal 三氟甲磺酸三甲基硅酯 、 氢气 作用下， 以 乙醇 、 二氯甲烷 为溶剂， 反应 6.75h， 生成 methyl 2-cyclopentyl-2-(formylamino)propanoate
  参考文献：
  名称：

  Synthesis of .alpha.-substituted .alpha.-amino acids via cationic intermediates

  摘要：

  A novel synthetic approach to racemic alpha-substituted alpha-amino acids is described. The key intermediates of this methodology are highly electrophilic iminium ions, bearing carbonyl substituents at both the iminium carbon and nitrogen atom. The preparation of precursors 8, 10a-c, and 12 includes electrochemical oxidation techniques according to literature procedures. When an alpha-methyl precursor (8 or 10a) was used, reactions with allylsilanes and silyl enol ethers led to the desired products, but elimination to dehydroalanine derivatives appeared to be an important side reaction. A major improvement in the yields of the desired products could be effected by using longer reaction times. In this way, efficient syntheses of protected alpha-methyl-alpha-amino acids could be developed. The elimination process appeared to be a more serious problem in the alpha-benzyl (10b) and alpha-allyl (10c) cases. On the other hand, the alpha-phenyl precursor 12 appeared to be highly useful, because the elimination is impossible in this case. High yields of alpha-phenyl-alpha-amino acid derivatives were obtained upon reaction of 12 with silicon-activated pi-nucleophiles. Deprotection led to various types of free alpha-substituted alpha-amino acids.

  DOI：

  10.1021/jo00064a011
• 作为产物：
  描述：

  在 silica gel 作用下， 以 乙醚 、 Petroleum ether 为溶剂， 生成 Methyl 2-formamido-2-(trimethylsiloxy)propanoate
  参考文献：
  名称：

  Synthesis of 1-acylamino-1-(trimethylsiloxy)alkanes by trimethylsilyl trifluoromethanesulfonate-catalysed addition of bis(trimethylsilyl)amides to aldehydes

  摘要：

  双(三甲基硅)甲酰胺在回流氯仿中与醛反应，或在室温下在三氟甲磺酸三甲基硅酯的催化下反应，生成 1-酰氨基-1-(三甲基硅氧基)烷烃；使用其他双（三甲基硅）酰胺也可以得到类似的结果，但令人惊讶的是，使用双（三甲基硅）乙酰胺却不能。

  DOI：

  10.1039/p19960000883

文献信息

• JOHNSON A. P.; LUKE R. W. A.; STEELE R. W., J. CHEM. SOC. CHEM. COMMUN.,(1986) N 22, 1658-1659
  作者：JOHNSON A. P.、 LUKE R. W. A.、 STEELE R. W.

  DOI：——

  日期：——
• Synthesis of .alpha.-substituted .alpha.-amino acids via cationic intermediates
  作者：Eric C. Roos、M. Carmen Lopez、Michael A. Brook、Henk Hiemstra、W. Nico Speckamp、Bernard Kaptein、Johan Kamphuis、Hans E. Schoemaker

  DOI：10.1021/jo00064a011

  日期：1993.6

  A novel synthetic approach to racemic alpha-substituted alpha-amino acids is described. The key intermediates of this methodology are highly electrophilic iminium ions, bearing carbonyl substituents at both the iminium carbon and nitrogen atom. The preparation of precursors 8, 10a-c, and 12 includes electrochemical oxidation techniques according to literature procedures. When an alpha-methyl precursor (8 or 10a) was used, reactions with allylsilanes and silyl enol ethers led to the desired products, but elimination to dehydroalanine derivatives appeared to be an important side reaction. A major improvement in the yields of the desired products could be effected by using longer reaction times. In this way, efficient syntheses of protected alpha-methyl-alpha-amino acids could be developed. The elimination process appeared to be a more serious problem in the alpha-benzyl (10b) and alpha-allyl (10c) cases. On the other hand, the alpha-phenyl precursor 12 appeared to be highly useful, because the elimination is impossible in this case. High yields of alpha-phenyl-alpha-amino acid derivatives were obtained upon reaction of 12 with silicon-activated pi-nucleophiles. Deprotection led to various types of free alpha-substituted alpha-amino acids.
• Synthesis of 1-acylamino-1-(trimethylsiloxy)alkanes by trimethylsilyl trifluoromethanesulfonate-catalysed addition of bis(trimethylsilyl)amides to aldehydes
  作者：A. Peter Johnson、Richard W. A. Luke、Robert W. Steele、Andrew N. Boa

  DOI：10.1039/p19960000883

  日期：——

  Bis(trimethylsilyl)formamide reacts with aldehydes in refluxing chloroform, or at room temperature with catalysis by trimethylsilyl trifluoromethanesulfonate, to give 1-acylamino-1-(trimethylsiloxy)alkanes; similar results are obtained with other bis(trimethylsilyl)amides, but surprisingly not with bis(trimethylsilyl)acetamide, and addition of bis(trimethylsilyl)formamide to ketones and acetals can also be accomplished using TMS triflate as catalyst.

  双(三甲基硅)甲酰胺在回流氯仿中与醛反应，或在室温下在三氟甲磺酸三甲基硅酯的催化下反应，生成 1-酰氨基-1-(三甲基硅氧基)烷烃；使用其他双（三甲基硅）酰胺也可以得到类似的结果，但令人惊讶的是，使用双（三甲基硅）乙酰胺却不能。