N-benzyloxycarbonyl-β-(2-bromophenyl)-α-dehydroalanine methyl ester | 445417-39-0

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂酸及其衍生物
• 英文名称: N-benzyloxycarbonyl-β-(2-bromophenyl)-α-dehydroalanine methyl ester
• 英文别名: (Z)-2-benzyloxycarbonylamino-3-(2-bromophenyl)-acrylic acid methyl ester；N-Cbz-β-(2-bromophenyl)-α-dehydroalanine methyl ester；methyl (Z)-2-(benzyloxycarbonyl)amino-3-(o-bromophenyl)acrylate；methyl (Z)-3-(2-bromophenyl)-2-(phenylmethoxycarbonylamino)prop-2-enoate
• CAS: 445417-39-0
• 化学式: C₁₈H₁₆BrNO₄
• 分子量: 390.233
• InChiKey: NYHXKBGXHPHKOW-WJDWOHSUSA-N

物化性质

• 沸点：
  508.5±50.0 °C(Predicted)
• 密度：
  1.432±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  24
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.11
• 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：

  N-benzyloxycarbonyl-β-(2-bromophenyl)-α-dehydroalanine methyl ester 在 palladium diacetate 氢气 、 potassium carbonate 、 三(邻甲基苯基)磷 作用下， 以 甲醇 、 乙二醇二甲醚 、 水 为溶剂， 80.0 ℃ 、448.16 kPa 条件下， 反应 24.0h， 生成 (S)-N^α-benzyloxycarbonyl-o-(1-naphthyl)phenylalanine methyl ester
  参考文献：
  名称：

  实用，不对称合成芳香族取代的大块和疏水色氨酸和苯丙氨酸衍生物

  摘要：

  芳香环取代的色氨酸和苯丙氨酸可以提供有价值的工具，以开发具有特定结构特征的强效和选择性肽配体，此外还可以提供一个大的亲脂性表面来与受体结合并穿越膜屏障。已经开发了合成这些新氨基酸的有效方法。在该方法中，使用Burk基于DuPHOS的Rh（I）催化剂进行α-酰胺的不对称氢化生成高对映体纯的α-氨基酸衍生物，随后将其与硼酸衍生物进行Suzuki交叉偶联，从而以高收率获得这些芳族取代的氨基酸和高对映选择性。该方法可以大规模制备此类氨基酸，以进行广泛的结构活性研究。

  DOI：

  10.1016/s0040-4020(02)00162-x
• 作为产物：
  描述：

  (±)-Z-α-膦酰甘氨酸三甲酯 、 邻溴苯甲醛 在 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以87%的产率得到N-benzyloxycarbonyl-β-(2-bromophenyl)-α-dehydroalanine methyl ester
  参考文献：
  名称：

  铜（I）催化的烯氨基甲酸酯的分子内环化：吲哚和吡咯并[2,3- c ]吡啶的合成

  摘要：

  在过去的几年中，通过芳基卤化物或三氟甲磺酸酯和胺的交叉偶联使用钯催化的芳香碳氮键形成反应已成为一种有用的合成工具。在这里，我们描述了一种铜（I）催化剂体系，该体系可以有效合成官能化的吲哚和吡咯并[2,3- c ]吡啶。该方法利用氨基酸促进的胺与芳基卤化物的铜偶联，特别是使用CuI-1-脯氨酸催化剂体系。

  DOI：

  10.1016/j.tetlet.2005.10.077

文献信息

• Palladium-catalyzed tandem C,N-arylation of immobilized enamine for solid phase indole synthesisElectronic supplementary information (ESI) available: experimental procedures. See http://www.rsc.org/suppdata/p1/b2/b206378f/
  作者：Kazuo Yamazaki、Yosuke Nakamura、Yoshinori Kondo

  DOI：10.1039/b206378f

  日期：2002.10.1

  Intramolecular palladium-catalyzed N-arylation of immobilized dehydrohalophenylalaninate was found to proceed smoothly to form indolecarboxylates. The method was successfully combined with the Heck reaction to perform one pot indole synthesis via palladium-catalyzed tandem C,N-arylation reactions.

  研究发现，固定化脱氢卤代苯丙氨酸的分子内钯催化 N-芳基化反应可顺利生成吲哚羧酸盐。该方法成功地与 Heck 反应相结合，通过钯催化串联 C、N-芳基化反应实现了一锅吲哚合成。
• Solid-Phase Synthesis of Indolecarboxylates Using Palladium-Catalyzed Reactions
  作者：Kazuo Yamazaki、Yosuke Nakamura、Yoshinori Kondo

  DOI：10.1021/jo0340307

  日期：2003.7.1

  Polymer-supported, palladium-catalyzed cyclization reactions effectively synthesized indolecarboxylates. Palladium-catalyzed carbon-carbon bond-forming reactions of immobilized enaminoesters followed by transesterification yielded indole 2- or 3-carboxylates with various functional groups on the benzene ring. Indolecarboxylates were efficiently cyclized via an intramolecular palladium-catalyzed amination reaction of immobilized N-substituted dehydrohalophenylalanines, and immobilized N-acetyl-dehydroalanines were efficiently converted into indolecarboxylates via tandem Heck-amination reactions.
• Design and synthesis of novel χ2-constrained phenylalanine, naphthylalanine, and tryptophan analogues and their use in biologically active melanotropin peptides
  作者：Wei Wang、Minying Cai、Chiyi Xiong、Junyi Zhang、Dev Trivedi、Victor J Hruby

  DOI：10.1016/s0040-4020(02)00588-4

  日期：2002.9

  A series of novel hydrophobic, bulky chi(2)-constrained phenylalanine, naphthylalanine, and tryptophan derivatives was designed and synthesized. The key steps involved asymmetric hydrogenations of alpha-enamides using Burk's DuPHOS-based Rh(l) catalysts to give high enantiomerically pure alpha-amino acid derivatives. The subsequent Suzuki cross couplings of the amino acid analogues with boronic acid derivatives afforded these aromatic substituted amino acids in high yields and with high enantioselectivity. The incorporation of these novel chi(2)-constrained amino acids into peptides and peptidomimetics provides fruitful information in the development of peptide and peptidomimetic ligands of melanotropins and an understanding of the interactions between ligands and receptors/acceptors. (C) 2002 Elsevier Science Ltd. All rights reserved.
• Design and synthesis of hydrophobic, bulky χ2-constrained phenylalanine and naphthylalanine derivatives
  作者：Wei Wang、Junyi Zhang、Chiyi Xiong、Victor J. Hruby

  DOI：10.1016/s0040-4039(02)00249-6

  日期：2002.3

  A series of novel hydrophobic, bulky chi(2)-constrained phenylalanine and naphthylalanine derivatives were designed and synthesized. Asymmetric hydrogenations of alpha-enamides using Burk's DuPHOS-based Rh(I) catalysts generated high enantiomerically pure alpha-amino acid derivatives, which subsequently underwent Suzuki cross couplings with boronic acid derivatives to afford these aromatic Substituted amino acids in high yields and with high enantioselectivity. (C) 2002 Elsevier Science Ltd. All rights reserved.