(2S,4R)-4-amino-pyrrolidine-1,2,4-tricarboxylic acid 1-benzyl ester 2-tert-butyl ester | 657412-45-8

• 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: (2S,4R)-4-amino-pyrrolidine-1,2,4-tricarboxylic acid 1-benzyl ester 2-tert-butyl ester
• 英文别名: (3R,5S)-3-amino-1-((benzyloxy)carbonyl)-5-(tert-butoxycarbonyl)pyrrolidine-3-carboxylic acid；(3R,5S)-3-amino-5-[(2-methylpropan-2-yl)oxycarbonyl]-1-phenylmethoxycarbonylpyrrolidine-3-carboxylic acid
• CAS: 657412-45-8
• 化学式: C₁₈H₂₄N₂O₆
• 分子量: 364.398
• InChiKey: BORLNKZZMQRGPU-SCLBCKFNSA-N

物化性质

• 熔点：
  255 °C (decomp)(Solv: methanol (67-56-1))
• 沸点：
  518.6±50.0 °C(Predicted)
• 密度：
  1.285±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -1.1
• 重原子数：
  26
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  119
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  (2S,4R)-4-amino-pyrrolidine-1,2,4-tricarboxylic acid 1-benzyl ester 2-tert-butyl ester 在 sodium cyanoborohydride 作用下， 以 甲醇 为溶剂， 反应 20.5h， 生成 (3R,5S)-3-(benzylamino)-5-[(2-methylpropan-2-yl)oxycarbonyl]-1-phenylmethoxycarbonylpyrrolidine-3-carboxylic acid
  参考文献：
  名称：

  Hydrophobic Substituent Effects on Proline Catalysis of Aldol Reactions in Water

  摘要：

  Derivatives of 4-hydroxyproline with a series of hydrophobic groups in well-defined orientations have been tested as catalysts for the aldol reactions. All of the modified proline catalysts carry out the intermolecular aldol reaction in water and provide high diastereoselectivity and enantioselectivity. Modified prolines with aromatic groups syn to the carboxylic acid are better catalysts than those with small hydrophobic groups (1a is 43.5 times faster than 1f). Quantum mechanical calculations provide transition structures, TS-1a(water) and TS-1f(water), that support the hypothesis that a stabilizing hydrophobic interaction occurs with 1a.

  DOI：

  10.1021/jo300569c
• 作为产物：
  描述：

  (5R,8S)-2,4-dioxo-1,3,7-triazaspiro[4.4]nonane-7,8-dicarboxylic acid 7-benzyl ester 8-tert-butyl ester 在 4-二甲氨基吡啶 、 potassium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 15.0h， 生成 (2S,4R)-4-amino-pyrrolidine-1,2,4-tricarboxylic acid 1-benzyl ester 2-tert-butyl ester
  参考文献：
  名称：

  一种改进的，可扩展的双氨基酸合成

  摘要：

  反式-4-羟基-1-脯氨酸衍生的双氨基酸是手性的环状结构单元，显示出两个带有保护基的α-氨基酸。它们被组装成螺线低聚物—刚性，形状可编程的螺环低聚物，在立体化学和功能上都不同。这里提出的合成集中在最近的改进上，这些改进允许从便宜的反式-4-羟基-1-脯氨酸方便，大规模地合成十二种立体化学纯的双氨基酸。双氨基酸在立体化学上和胺保护基上有所不同，其中一个（对硝基苄基氨基甲酸酯）以前没有被掺入双氨基酸中。

  DOI：

  10.1016/j.tetlet.2016.09.032

文献信息

• Bis (amino acid) molecular scaffolds
  申请人：——

  公开号：US20040077879A1

  公开（公告）日：2004-04-22

  The present invention provides molecular building blocks of rigid bis(amino acids). The molecular building blocks can be linked together through the formation of rigid diketopiperazine rings, to provide the desired three dimensional structure. Also provided is method of synthesizing macromolecules from the bis (amino acid) building blocks.

  本发明提供了刚性双(氨基酸)的分子构建模块。这些分子构建模块可以通过形成刚性二酮二肽环相互连接，以提供所需的三维结构。同时提供了一种从双(氨基酸)构建模块合成高分子的方法。
• Development of Fmoc-Protected Bis-Amino Acids toward Automated Synthesis of Highly Functionalized Spiroligomers
  作者：Yihui Xie、Danni Luo、Jesse Wiener、Sicheng Tang、Sergiy Chepyshev、Christian Schafmeister

  DOI：10.1021/acs.orglett.2c01295

  日期：2022.5.13

  multikilogram-scale synthesis of bis-amino acid precursors. This allows the synthesis of stereochemically and functionally diverse spiroligomers utilizing solid-phase Fmoc/tBu chemistry to facilitate the development of applications. Four tetramers were assembled on a semiautomated microwave peptide synthesizer. We determined their secondary structures with two-dimensional nuclear magnetic resonance spectroscopy.

  我们报告了使用临时 Cu 2+络合策略以及双氨基酸前体的高效多千克规模合成功能化双氨基酸构建块的芴基甲氧基羰基 (Fmoc) 保护。这允许利用固相 Fmoc/tBu 化学合成立体化学和功能多样的螺旋低聚物，以促进应用的开发。在半自动微波肽合成仪上组装了四个四聚体。我们用二维核磁共振波谱确定了它们的二级结构。
• Spiroligozymes for Transesterifications: Design and Relationship of Structure to Activity
  作者：Mahboubeh Kheirabadi、Nihan Çelebi-Ölçüm、Matthew F. L. Parker、Qingquan Zhao、Gert Kiss、K. N. Houk、Christian E. Schafmeister

  DOI：10.1021/ja3069648

  日期：2012.11.7

  Transesterification catalysts based. on stereochemically defined, modular, functionalized ladder-molecules (named spiroligozymes) were designed, using the "inside-out" design strategy, and mutated synthetically to improve catalysis. A series of stereochemically and regiochemically diverse bifunctional spiroligozymes were first synthesized to identify the best arrangement of a pyridine as a general base catalyst and an alcohol nucleophile to accelerate attack on vinyl trifluoroacetate as an electrophile. The best bifunctional spiroligozyme reacted with vinyl trifluoroacetate to form an acyl-spiroligozyme conjugate 2.7 X 10(3)-fold faster than the background reaction with a benzyl alcohol. Two trifunctional spiroligozymes were then synthesized that combined a urea with the pyridine and alcohol to act as an oxyanion hole and activate the bound acyl-spiroligozyme intermediate to enable acyl-transfer to methanol. The best trifunctional spiroligozyme carries out multiple turnovers and acts as a transesterification catalyst with k(1)/k(uncat) of 2.2 X 10(3) and k(2)/k(uncat) of 1.3 X 10(2). Quantum mechanical calculations identified the four transition states of the catalytic cycle and provided a detailed view of every stage of the transesterification reaction.
• Maximizing the Stereochemical Diversity of Spiro-Ladder Oligomers
  作者：Christopher G. Levins、Zachary Z. Brown、Christian E. Schafmeister

  DOI：10.1021/ol060902q

  日期：2006.6.1

  We introduce all stereoisomers of a bis-amino acid building block derived from trans-4-hydroxy-L-proline. This small library of monomers allows arbitrary stereochemical configuration at any chiral center within our spiro-ladder oligomers. Three tetramer oligomers containing several combinations of the monomers 1-4 were synthesized; we explored the effect of monomer sequence on scaffold conformation by NMR.
• Architectural Spiroligomers Designed for Binuclear Metal Complex Templating
  作者：Shivaiah Vaddypally、Chongsong Xu、Senzhi Zhao、Yanfeng Fan、Christian E. Schafmeister、Michael J. Zdilla

  DOI：10.1021/ic4003498

  日期：2013.6.3

  The first structurally, spectroscopically, and electronically characterized metal-spiroligomer complexes are reported. The binuclear [M2L2](4+) ions (M = Mn, Zn) are macrocyclic "squares" and are characterized by X-ray diffraction, H-1 and C-13 NMR, electronic absorption, emission, and mass spectroscopies. The manganese complex contains two spin-independent Mn-II ions and is additionally characterized using EPR and CD spectroscopies and CV.