2-((Allyloxycarbonyl)amino)-N-methoxy-4-pentenamide | 145275-85-0

• 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: 2-((Allyloxycarbonyl)amino)-N-methoxy-4-pentenamide
• 英文别名: Alloc-All-NHOMe；2-<(Allyloxycarbonyl)amino>-N-methoxy-4-pentenamide；prop-2-enyl N-[1-(methoxyamino)-1-oxopent-4-en-2-yl]carbamate
• CAS: 145275-85-0
• 化学式: C₁₀H₁₆N₂O₄
• 分子量: 228.248
• InChiKey: JSKPBNFQBWDCEO-UHFFFAOYSA-N

物化性质

• 密度：
  1.093±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  16
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  76.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  2-((Allyloxycarbonyl)amino)-N-methoxy-4-pentenamide 在 四(三苯基膦)钯 氢氧化钾 、 三正丁基氢锡 、 苯甲醛 作用下， 以 二氯甲烷 为溶剂， 反应 23.25h， 生成 (S)-(-)-2-氨基-4-戊烯酸
  参考文献：
  名称：

  Synthesis of racemic .alpha.-amino carboxamides via Lewis acid-mediated reactions of .alpha.-methoxyglycinamide derivatives with allylsilanes: enzymic resolution to optically active .alpha.-amino acids

  摘要：

  A short and expedient synthetic route to optically active, saturated and gamma,delta-unsaturated alpha-amino acids is reported. The key step is a BF3.OEt2-mediated reaction of allylsilanes with N-(alkoxycarbonyl)-alpha-methoxyglycinamides 11-15, leading to the corresponding gamma,delta-unsaturated alpha-aminocarboxamides. The genuine S(N)1-character of this process with iminium ion 6 as intermediate is proven in the case of the glycine ester 10. Thus, reaction of enzymatically resolved 10 with pi-nucleophiles leads to racemic products. The most useful iminium precursors are the N-methoxyamides 12-14 providing good yields of coupling products. The most convenient N-protective group is the allyloxycarbonyl group. Deprotection proceeds via a Pd(0)-catalyzed transprotection to the corresponding BOC-protected analogues. Four examples of the enzymatic resolution of alpha-amino carboxamides, by using an L-specific aminopeptidase from Pseudomonas putida, are described in detail. Most notably, secondary N-methoxyamides are good substrates for the enzyme to provide the desired a-amino acids in high optical purity.

  DOI：

  10.1021/jo00051a019
• 作为产物：
  描述：

  2-((Allyloxycarbonyl)amino)-2-methoxy-N-methoxyacetamide 、 烯丙基三甲基硅烷 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到2-((Allyloxycarbonyl)amino)-N-methoxy-4-pentenamide
  参考文献：
  名称：

  Synthesis of racemic .alpha.-amino carboxamides via Lewis acid-mediated reactions of .alpha.-methoxyglycinamide derivatives with allylsilanes: enzymic resolution to optically active .alpha.-amino acids

  摘要：

  A short and expedient synthetic route to optically active, saturated and gamma,delta-unsaturated alpha-amino acids is reported. The key step is a BF3.OEt2-mediated reaction of allylsilanes with N-(alkoxycarbonyl)-alpha-methoxyglycinamides 11-15, leading to the corresponding gamma,delta-unsaturated alpha-aminocarboxamides. The genuine S(N)1-character of this process with iminium ion 6 as intermediate is proven in the case of the glycine ester 10. Thus, reaction of enzymatically resolved 10 with pi-nucleophiles leads to racemic products. The most useful iminium precursors are the N-methoxyamides 12-14 providing good yields of coupling products. The most convenient N-protective group is the allyloxycarbonyl group. Deprotection proceeds via a Pd(0)-catalyzed transprotection to the corresponding BOC-protected analogues. Four examples of the enzymatic resolution of alpha-amino carboxamides, by using an L-specific aminopeptidase from Pseudomonas putida, are described in detail. Most notably, secondary N-methoxyamides are good substrates for the enzyme to provide the desired a-amino acids in high optical purity.

  DOI：

  10.1021/jo00051a019

文献信息

• Palladium-Catalyzed Transprotection of Allyloxycarbonyl-Protected Amines: Efficient One-Pot Formation of Amides and Dipeptides
  作者：Eric C. Roos、Pablo Bernabe、Henk Hiemstra、W. Nico Speckamp、Bernard Kaptein、Wilhelmus H. J. Boesten

  DOI：10.1021/jo00111a035

  日期：1995.3

  The synthetic utility of the N-(allyloxycarbonyl) (Alloc) substituent in alpha-amino acid derivatives is substantially extended beyond its well-known function as an amine protecting group. When the palladium-catalyzed deprotection is carried out by using tributyltin hydride as nucleophile (the Guibe method) in the presence of an active acylating agent a new acyl group is introduced on nitrogen. Successful acylating agents include carboxylic acid anhydrides, acid chlorides, and activated esters. A useful example of this methodology is the removal of the Alloc group in the presence of tert-butyl dicarbonate, which in essence amounts to a ''transprotection'' to a Boc-protected alpha-amino acid derivative. More importantly, the use of activated N-protected alpha-amino ester derivatives (e.g., pentafluorophenyl esters) leads to dipeptides. This new method for peptide coupling proceeds very fast under mild conditions, in good to excellent yields, and without noticeable racemization.
• Palladium-catalyzed synthesis of amides and peptides
  作者：Eric C. Roos、Pablo Bernabé、Henk Hiemstra、W.Nico Speckamp、Bernard Kaptein、Wilhelmus H.J. Boesten

  DOI：10.1016/0040-4039(91)80241-w

  日期：1991.11

  When the Pd(0)-catalyzed hydrostannolysis of the N-allyloxycarbonyl group is carried out in the presence of an activated carbonyl compound, a coupling product is formed. This new method appears to be applicable to the synthesis of a wide range of amides and peptides.
• Synthesis of racemic .alpha.-amino carboxamides via Lewis acid-mediated reactions of .alpha.-methoxyglycinamide derivatives with allylsilanes: enzymic resolution to optically active .alpha.-amino acids
  作者：Eric C. Roos、Hendrik H. Mooiweer、Henk Hiemstra、W. Nico Speckamp、Bernard Kaptein、Wilhelmus H. J. Boesten、Johan Kamphuis

  DOI：10.1021/jo00051a019

  日期：1992.12

  A short and expedient synthetic route to optically active, saturated and gamma,delta-unsaturated alpha-amino acids is reported. The key step is a BF3.OEt2-mediated reaction of allylsilanes with N-(alkoxycarbonyl)-alpha-methoxyglycinamides 11-15, leading to the corresponding gamma,delta-unsaturated alpha-aminocarboxamides. The genuine S(N)1-character of this process with iminium ion 6 as intermediate is proven in the case of the glycine ester 10. Thus, reaction of enzymatically resolved 10 with pi-nucleophiles leads to racemic products. The most useful iminium precursors are the N-methoxyamides 12-14 providing good yields of coupling products. The most convenient N-protective group is the allyloxycarbonyl group. Deprotection proceeds via a Pd(0)-catalyzed transprotection to the corresponding BOC-protected analogues. Four examples of the enzymatic resolution of alpha-amino carboxamides, by using an L-specific aminopeptidase from Pseudomonas putida, are described in detail. Most notably, secondary N-methoxyamides are good substrates for the enzyme to provide the desired a-amino acids in high optical purity.