α-allylphenylalaninamide | 133230-55-4

• 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: α-allylphenylalaninamide
• 英文别名: 2-Amino-2-benzylpent-4-enamide
• CAS: 133230-55-4
• 化学式: C₁₂H₁₆N₂O
• 分子量: 204.272
• InChiKey: RBKGHHJYVHUWSS-UHFFFAOYSA-N

物化性质

• 熔点：
  120-121 °C
• 沸点：
  381.5±42.0 °C(Predicted)
• 密度：
  1.087±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  69.1
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  α-allylphenylalaninamide 在 N-甲基吗啉 、 bis(cyclohexanyl)borane 、 双氧水 、 氯甲酸异丁酯 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 N-(Boc-Asp(OBn))-α-(3-hydroxy-n-propyl)phenylalaninamide
  参考文献：
  名称：

  Synthesis of .alpha.-benzyl .gamma.-lactam, .alpha.-benzyl .delta.-lactam, and .alpha.-benzylproline derivatives as conformationally restricted analogs of phenylalaninamide

  摘要：

  The ready availability of N-(trifluoroacetyl)-alpha-allylphenylalaninamide (4) via a dehydration/hetero-Cope rearrangement/ammonolysis sequence starting with N-(trifluoroacetyl)phenylalanine allyl ester made it an attractive intermediate for elaboration into C-alpha to N- or C-alpha to N'bridged products as conformationally restricted phenylalaninamide analogues. Oxidative one-carbon degradation of the side-chain olefin followed by acid-catalyzed silane reduction afforded C-alpha to N'-bridged gamma-lactam. Hydroboration/oxidation of the side-chain olefin provided an intermediate that could be cyclized selectively either to a delta-lactam or a proline analogue depending on choice of dehydrating conditions. For preparation of a target dipeptide containing the alpha-substituted proline moiety, a preferred route involved N-deprotection of 4 and coupling to Boc-Asp(OBn)-OH to give a dipeptide intermediate, which similarly could be elaborated selectively to either the alpha-benzyl delta-lactam analogue or the alpha-benzylproline analogue.

  DOI：

  10.1021/jo00012a022
• 作为产物：
  描述：

  N-(trifluoroacetyl)-α-allylphenylalaninamide 在 盐酸 、 barium dihydroxide 作用下， 以 甲醇 为溶剂， 生成 α-allylphenylalaninamide
  参考文献：
  名称：

  Synthesis of .alpha.-benzyl .gamma.-lactam, .alpha.-benzyl .delta.-lactam, and .alpha.-benzylproline derivatives as conformationally restricted analogs of phenylalaninamide

  摘要：

  The ready availability of N-(trifluoroacetyl)-alpha-allylphenylalaninamide (4) via a dehydration/hetero-Cope rearrangement/ammonolysis sequence starting with N-(trifluoroacetyl)phenylalanine allyl ester made it an attractive intermediate for elaboration into C-alpha to N- or C-alpha to N'bridged products as conformationally restricted phenylalaninamide analogues. Oxidative one-carbon degradation of the side-chain olefin followed by acid-catalyzed silane reduction afforded C-alpha to N'-bridged gamma-lactam. Hydroboration/oxidation of the side-chain olefin provided an intermediate that could be cyclized selectively either to a delta-lactam or a proline analogue depending on choice of dehydrating conditions. For preparation of a target dipeptide containing the alpha-substituted proline moiety, a preferred route involved N-deprotection of 4 and coupling to Boc-Asp(OBn)-OH to give a dipeptide intermediate, which similarly could be elaborated selectively to either the alpha-benzyl delta-lactam analogue or the alpha-benzylproline analogue.

  DOI：

  10.1021/jo00012a022

文献信息

• Synthesis of α,α-disubstituted α-amino acid amides by phase-transfer catalyzed alkylation
  作者：Bernard Kaptein、Wilhelmus H.J. Boesten、Quirinus B. Broxterman、Hans E. Schoemaker、Johan Kamphuis

  DOI：10.1016/s0040-4039(00)61112-7

  日期：1992.9

  α,α-Disubstituted α-amino acid amides were prepared in 17–86% chemical yield by the phase-transfer catalyzed alkylation of N-benzylidene α-H amino acid amides, followed by weak acidic hydrolysis of the Schiff bases.

  通过相转移催化N-亚苄基α-H氨基酸酰胺的烷基化反应，然后对席夫碱进行弱酸性水解，可以制备出化学产率为17-86％的α，α-二取代的α-氨基酸酰胺。
• Synthesis of enantiomerically pure 2,2-disubstituted-2-amino-ethanols by dissolving metal reduction of a,a-disubstituted amino acid amides
  作者：Harold M. Moody、Bernard Kaptein、Quirinus B. Broxterman、Wilhelmus H.J. Boesten、Johan Kamphuis

  DOI：10.1016/0040-4039(94)88344-0

  日期：1994.3

  Enantiomerically pure 2,2-disubstituted 2-amino-ethanols are prepared in 65 – 99% yield by reduction of a,a-disubstituted amino acid amides using liquid sodium metal in refluxing 1-propanol.

  对映体纯的2,2-二取代的2-氨基乙醇在65制备-通过还原的产率99％一，一个在回流的1-丙醇二取代使用液态钠金属氨基酸酰胺。
• Enzymatic resolution of α,α-disubstituted α-amino acid esters and amides
  作者：Bernard Kaptein、Wilhelmus H.J. Boesten、Quirinus B. Broxterman、Pfet J.H. Peters、Hans E. Schoemaker、Johan Kamphuis

  DOI：10.1016/s0957-4166(00)80217-7

  日期：1993.6

  The scope and limitations of the enzymatic resolution of alpha,alpha-disubstituted alpha-amino acid amides by an amino acid amidase from Mycobacterium neoaurum and of the corresponding ethyl esters with Pig liver esterase (PLE) have been studied. Moderate enantiomeric excesses were obtained with PLE, with only a narrow substrate specificity. Mycobacterium neoaurum on the contrary yields a broad range of S-alpha,alpha-disubstituted alpha-amino acids 1 and the corresponding R-amides 2.
• HOLLADAY, M. W.;NADZAN, A. M., J. ORG. CHEM., 56,(1991) N2, C. 3900-3905
  作者：HOLLADAY, M. W.、NADZAN, A. M.

  DOI：——

  日期：——
• Moody Harold M., Kaptein Bernard, Broxterman Quirinus B., Boesten Wilhelm+, Tetrahedron Lett, 35 (1994) N 11, S 1777-1780
  作者：Moody Harold M., Kaptein Bernard, Broxterman Quirinus B., Boesten Wilhelm+

  DOI：——

  日期：——