N-acetyl-L-leucine p-nitrophenyl ester | 14009-96-2

• 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: N-acetyl-L-leucine p-nitrophenyl ester
• 英文别名: p-Nitrophenyl N-acetyl-L-leucinat；(4-nitrophenyl) (2S)-2-acetamido-4-methylpentanoate
• CAS: 14009-96-2
• 化学式: C₁₄H₁₈N₂O₅
• 分子量: 294.307
• InChiKey: KORBUAHWVTZISR-ZDUSSCGKSA-N

物化性质

• 沸点：
  499.3±30.0 °C(Predicted)
• 密度：
  1.203±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  21
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  N-acetyl-L-leucine p-nitrophenyl ester 、 叔丁胺 反应 0.67h， 生成 (S)-2-acetamido-N-(tert-butyl)-4-methylpentanamide
  参考文献：
  名称：

  环境自由基氧化剂NO 3 •对脂族氨基酸，二肽和三肽的氧化损伤：动力学和计算研究揭示酰胺键的作用

  摘要：

  动力学和计算数据表明，重要的环境自由基氧化剂NO 3 •在与脂肪族氨基酸以及二肽和三肽的反应中具有复杂的行为，这表明对肽主链中酰胺N–H键的攻击是高度可行的途径，这是通过质子耦合电子转移（PCET）机理进行的，在乙腈中的速率系数约为1×10 6 M –1 s –1。确定了类似的速率系数，用于确定侧链中α-碳和叔C–H键的夺氢作用。获得的NO 3 •反应速率系数带有脂族二肽和三肽的化合物表明，攻击在每个氨基酸残基的所有这些位点发生，这使得脂族肽序列极易受到NO 3 •诱导的氧化损伤的影响。NO 3 •与脂肪族肽中侧链的反应没有发现酰胺邻基效应的证据，酰胺邻基效应先前已发现可促进自由基诱导的苯丙氨酸侧链破坏。

  DOI：

  10.1021/acs.joc.8b03224
• 作为产物：
  描述：

  L-正缬氨酸 在 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 生成 N-acetyl-L-leucine p-nitrophenyl ester
  参考文献：
  名称：

  环境自由基氧化剂NO 3 •对脂族氨基酸，二肽和三肽的氧化损伤：动力学和计算研究揭示酰胺键的作用

  摘要：

  动力学和计算数据表明，重要的环境自由基氧化剂NO 3 •在与脂肪族氨基酸以及二肽和三肽的反应中具有复杂的行为，这表明对肽主链中酰胺N–H键的攻击是高度可行的途径，这是通过质子耦合电子转移（PCET）机理进行的，在乙腈中的速率系数约为1×10 6 M –1 s –1。确定了类似的速率系数，用于确定侧链中α-碳和叔C–H键的夺氢作用。获得的NO 3 •反应速率系数带有脂族二肽和三肽的化合物表明，攻击在每个氨基酸残基的所有这些位点发生，这使得脂族肽序列极易受到NO 3 •诱导的氧化损伤的影响。NO 3 •与脂肪族肽中侧链的反应没有发现酰胺邻基效应的证据，酰胺邻基效应先前已发现可促进自由基诱导的苯丙氨酸侧链破坏。

  DOI：

  10.1021/acs.joc.8b03224

文献信息

• Preparation of N-acetyl, tert-butyl amide derivatives of the 20 natural amino acids
  作者：A. R. Ekkati、A. A. Campanali、A. I. Abouelatta、M. Shamoun、S. Kalapugama、M. Kelley、Jeremy J. Kodanko

  DOI：10.1007/s00726-009-0279-y

  日期：2010.3

  N-Acetyl-AA(amino acid)-NHtBu derivatives of all 20 naturally occurring amino acids have been synthesized. Syntheses were performed via solution-phase methodology with yields that allow for access to gram quantities of substrates, in most cases. Syntheses include the coupling of a hindered amine, tert-butylamine, with each amino acid, either directly or in two steps using an activated ester isolated as an intermediate. The introduction of protecting groups was necessary in some cases. The development of synthetic sequences to access challenging substrates, such as the one derived from asparagine, are discussed.
• Investigations of an Antibody Ligase
  作者：David B. Smithrud、Patricia A. Benkovic、Stephen J. Benkovic、Carol M. Taylor、Kraig M. Yager、Jason Witherington、Barton W. Philips、Paul A. Sprengeler、Amos B. Smith、Ralph Hirschmann

  DOI：10.1021/ja963167u

  日期：1997.1.1

  Further investigation of the monoclonal antibody 16G3 has revealed that it not only couples activated amino acids to form dipeptides with high turnover rates but also couples an activated amino acid with a dipeptide to form a tripeptide, as well as an activated dipeptide with another dipeptide to give a tetrapeptide. The catalytic rates for these reactions greatly exceed the background rate of ester hydrolysis providing average yields of 80% within the assay time of 20 min. Importantly, the amount of product inhibition is low, allowing for high yields of products using multiple addition of substrates to the same antibody reaction mixture. A sequential mechanism is employed by 16G3 for dipeptide coupling, and this mechanism appears to hold for the formation of the other peptides. High catalytic selectivity is observed for the nucleophilic alpha-amino group of an alpha,beta-diamino nucleophile and for the para substituent on the activated ester, traits that are consistent with hapten design. The former chemoselectivity is crucial for the condensation of fragments which are unprotected at the epsilon-amino group of lysine.
• Oxidative Damage in Aliphatic Amino Acids and Di- and Tripeptides by the Environmental Free Radical Oxidant NO₃^•: The Role of the Amide Bond Revealed by Kinetic and Computational Studies
  作者：Joses G. Nathanael、Uta Wille

  DOI：10.1021/acs.joc.8b03224

  日期：2019.3.15

  free radical oxidant NO3• in its reactions with aliphatic amino acids and di- and tripeptides, suggesting that attack at the amide N–H bond in the peptide backbone is a highly viable pathway, which proceeds through a proton-coupled electron transfer (PCET) mechanism with a rate coefficient of about 1 × 106 M–1 s–1 in acetonitrile. Similar rate coefficients were determined for hydrogen abstraction from

  动力学和计算数据表明，重要的环境自由基氧化剂NO 3 •在与脂肪族氨基酸以及二肽和三肽的反应中具有复杂的行为，这表明对肽主链中酰胺N–H键的攻击是高度可行的途径，这是通过质子耦合电子转移（PCET）机理进行的，在乙腈中的速率系数约为1×10 6 M –1 s –1。确定了类似的速率系数，用于确定侧链中α-碳和叔C–H键的夺氢作用。获得的NO 3 •反应速率系数带有脂族二肽和三肽的化合物表明，攻击在每个氨基酸残基的所有这些位点发生，这使得脂族肽序列极易受到NO 3 •诱导的氧化损伤的影响。NO 3 •与脂肪族肽中侧链的反应没有发现酰胺邻基效应的证据，酰胺邻基效应先前已发现可促进自由基诱导的苯丙氨酸侧链破坏。