C^α-methyl-D,L-allylglycinamide | 144125-67-7

• 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: C^α-methyl-D,L-allylglycinamide
• 英文别名: (RS)-2-amino-2-methyl-4-pentenoic acid amide；D,L-2-amino-2-methyl-4-pentenoic acid amide；alpha-methyl-alpha-allylgylcine amide；C^α-methyl-D,L-allylglycine amide；2-Amino-2-methylpent-4-enamide
• CAS: 144125-67-7
• 化学式: C₆H₁₂N₂O
• mdl: MFCD19204089
• 分子量: 128.174
• InChiKey: YERSGVQSBHBTNK-UHFFFAOYSA-N

物化性质

• 沸点：
  244.5±40.0 °C(Predicted)
• 密度：
  1.007±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  C^α-methyl-D,L-allylglycinamide 在 氢氧化钾 、 Mycobacterium neoaurum 、 溶剂黄146 作用下， 反应 20.0h， 生成 (R)-(+)-α-烯丙基丙氨酸
  参考文献：
  名称：

  MAG：一个C α甲基化的，侧链不饱和α氨基酸。模型肽和构象偏好介绍

  摘要：

  通过化学-酶促的方法，我们合成中的手性，C α甲基化的α氨基酸MAG，其特征在于，一个侧链C γ C δ键。我们还制备了一系列含有Mag以及Aib和Ala的模型肽，并对所有肽进行了充分表征，并通过FT-IR吸收和1 H NMR研究了它们在溶液中的构象偏好。还介绍了l-Mag，一种衍生物和三种肽的X射线衍射分析。我们发现，该C α甲基化的α氨基酸是优良的β转角和3 10螺旋前者。完整旋转3 10后，带有两个Mag残基的肽一个在另一个的顶部-螺旋已经合成并表征。

  DOI：

  10.1016/s0040-4020(00)00274-x
• 作为产物：
  描述：

  N-benzylidene-DL-alanine amide 、 3-溴丙烯 生成 C^α-methyl-D,L-allylglycinamide
  参考文献：
  名称：

  Synthesis of (optically active) sulfur-containing trifunctional amino acids by radical addition to (optically active) unsaturated amino acids

  摘要：

  Sulfur-based radicals, generated from R-S-H-type precursors (R = alkyl, acyl) with AIBN, smoothly add to alpha-allylglycines protected at none, one, or both of the amino acid functions (NH2 and/or CO2H). Sulfur-containing trifunctional amino acids were obtained in good to excellent yields (64-100%). The solvent used for the reaction is critical. Optimal results were obtained when both the unsaturated amino acid and RSH dissolve completely in the medium (dioxane/water or methanol/water are good solvent systems). The scope of the reaction includes alpha-substituted alpha-allylglycine and derivatives as well as beta-substituted beta-allyl-beta-ammo alcohols. In the case of optically active alpha-allylglycine derivatives, radical addition is accompanied by a small amount of racemization, the amount depending on the type of protection and R-S-H. The products are easily optically enriched by crystallization. Addition of sulfur-based radicals to alpha-allylglycine is believed to be an example of a general method for synthesizing optically active trifunctional amino acids from unsaturated amino acids.

  DOI：

  10.1021/jo00049a041

文献信息

• A Cross-Metathesis Route to Functionalized α-Methyl α-Substituted Amino Acids
  作者：Roy P. M. Storcken、Lavinia Panella、Floris L. van Delft、Bernard Kaptein、Quirinus B. Broxterman、Hans E. Schoemaker、Floris P. J. T. Rutjes

  DOI：10.1002/adsc.200600446

  日期：2007.1.8

  A chemoenzymatic approach to the synthesis of functionalized α-methyl α-substituted amino acids is detailed. This involves amidase-mediated enzymatic resolution of α-methyl α-substituted side-chain ω-unsaturated amino acids followed by functionalization via cross-metathesis.

  用化学酶方法合成功能化的α-甲基α-取代的氨基酸。这涉及酰胺酶介导的α-甲基α-取代的侧链ω-不饱和氨基酸的酶促拆分，然后通过交叉复分解进行功能化。
• 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。
• 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.
• Enantiopure Cα-tetrasubstituted α-amino acids. Chemo-enzymatic synthesis and application to turn-forming peptides
  作者：Bernard Kaptein、Quirinus B Broxterman、Hans E Schoemaker、Floris P.J.T Rutjes、Johan J.N Veerman、Johan Kamphuis、Cristina Peggion、Fernando Formaggio、Claudio Toniolo

  DOI：10.1016/s0040-4020(01)00548-8

  日期：2001.7

  By a chemo-enzymatic approach we carried out a large-scale synthesis of four enantiopure, sterically constrained, C-alpha-tetra-substituted alpha -amino acids, all characterized by a sidechain (CCdelta)-C-gamma double bond. By using one of them (L-Mag), we prepared an N-alpha-protected tetrapeptide benzylamide which was shown to adopt a beta -turn conformation and to efficiently undergo ring-closing olefin metathesis. (C) 2001 Elsevier Science Led. All rights reserved.
• Synthesis of (optically active) sulfur-containing trifunctional amino acids by radical addition to (optically active) unsaturated amino acids
  作者：Quirinus B. Broxterman、Bernard Kaptein、Johan Kamphuis、Hans E. Schoemaker

  DOI：10.1021/jo00049a041

  日期：1992.11

  Sulfur-based radicals, generated from R-S-H-type precursors (R = alkyl, acyl) with AIBN, smoothly add to alpha-allylglycines protected at none, one, or both of the amino acid functions (NH2 and/or CO2H). Sulfur-containing trifunctional amino acids were obtained in good to excellent yields (64-100%). The solvent used for the reaction is critical. Optimal results were obtained when both the unsaturated amino acid and RSH dissolve completely in the medium (dioxane/water or methanol/water are good solvent systems). The scope of the reaction includes alpha-substituted alpha-allylglycine and derivatives as well as beta-substituted beta-allyl-beta-ammo alcohols. In the case of optically active alpha-allylglycine derivatives, radical addition is accompanied by a small amount of racemization, the amount depending on the type of protection and R-S-H. The products are easily optically enriched by crystallization. Addition of sulfur-based radicals to alpha-allylglycine is believed to be an example of a general method for synthesizing optically active trifunctional amino acids from unsaturated amino acids.