Leucine p-nitrophenyl ester | 17663-34-2

• 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: Leucine p-nitrophenyl ester
• 英文别名: Leucin-p-nitro-phenylester；(4-Nitrophenyl) 2-amino-4-methylpentanoate
• CAS: 17663-34-2；66575-12-0
• 化学式: C₁₂H₁₆N₂O₄
• 分子量: 252.27
• InChiKey: JLYJVSOKGRWLFG-UHFFFAOYSA-N

物化性质

• 沸点：
  387.2±27.0 °C(Predicted)
• 密度：
  1.204±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  98.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  Leucine p-nitrophenyl ester 在 (R)-<methyl>pyridine 、 铜 作用下， 以 various solvent(s) 为溶剂， 生成 D-亮氨酸 、 L-亮氨酸
  参考文献：
  名称：

  Chiral Lipophilic Ligands. 1. Enantioselective Cleavage of .alpha.-Amino Acid Esters in Metallomicellar Aggregates

  摘要：

  Several chiral ligands (1a,b, 2a-d), their marked lipophilic structure featuring a binding subunit comprising a 2-substituted pyridine, a tertiary amine, and a hydroxyl, have been synthesized and their complexes with Cu(II), Zn(II), or Co(II) ions investigated in homomicellar or comicellar aggregates as enantioselective catalysts of the cleavage of p-nitrophenyl esters of alpha-amino acids (Phe, Phg, Leu). Rate accelerations up to 3 orders of magnitude over the Cu(II) catalyzed hydrolysis and enantioselectivities ranging from; 3.2 to 11.6 have been observed. In each case explored, the chiral ligand reacts faster with the enantiomeric substrate of opposite absolute configuration. Several pieces of evidence indicate that the effective cleavage process in micellar aggregates involves the following: (a) the formation of a ternary (ligand-metal ion-substrate) complex; (b) within such a complex, a nucleophilic attack of the ligand hydroxyl on the substrate to give a transacylation intermediate; and (c) the metal ion promoted hydrolysis of the transacylation intermediate with a relatively fast turnover of the catalyst. Such a mode of action does not operate outside or in the absence of micellar aggregates: in this case; the hydroxyl is displaced by water that acts as the nucleophile ina slower (less enantioselective) process. The enantioselectivity of the transacylation process appears to be little affected by the steric interaction between the substituents at the chiral center of the amino acid ester and of the ligand. We suggest that the enantioselectivity arises from a different hydration, due to steric reasons, of the diastereomeric complexes comprising the two enantiomers of the substrate. As a consequence, the relevance of the competing mechanisms of cleavage of the ester, the first one, faster, involving the hydroxyl and the second one, slower, involving a Cu(II)-bound water molecule, may be different. In the case of the less hydrated, more hydrophobic R-S or S-R complex the former, faster, mode of cleavage may be more relevant than in the case of the more hydrated, less hydrophobic, S-S or R-R complex.

  DOI：

  10.1021/jo00094a034

文献信息

• HENKLEIN, P.;JAHRLING, RENATE;HOFMANN, KATHRIN;NIEDRICH, H.;OTT, T., PHARMAZIE, 43,(1988) N2, C. 862
  作者：HENKLEIN, P.、JAHRLING, RENATE、HOFMANN, KATHRIN、NIEDRICH, H.、OTT, T.

  DOI：——

  日期：——
• Glucosamine-peptide derivatives, their production and use
  申请人：Takeda Chemical Industries, Ltd.

  公开号：EP0014984B1

  公开（公告）日：1982-12-01
• Chiral Lipophilic Ligands. 1. Enantioselective Cleavage of .alpha.-Amino Acid Esters in Metallomicellar Aggregates
  作者：Paolo Scrimin、Paolo Tecilla、Umberto Tonellato

  DOI：10.1021/jo00094a034

  日期：1994.7

  Several chiral ligands (1a,b, 2a-d), their marked lipophilic structure featuring a binding subunit comprising a 2-substituted pyridine, a tertiary amine, and a hydroxyl, have been synthesized and their complexes with Cu(II), Zn(II), or Co(II) ions investigated in homomicellar or comicellar aggregates as enantioselective catalysts of the cleavage of p-nitrophenyl esters of alpha-amino acids (Phe, Phg, Leu). Rate accelerations up to 3 orders of magnitude over the Cu(II) catalyzed hydrolysis and enantioselectivities ranging from; 3.2 to 11.6 have been observed. In each case explored, the chiral ligand reacts faster with the enantiomeric substrate of opposite absolute configuration. Several pieces of evidence indicate that the effective cleavage process in micellar aggregates involves the following: (a) the formation of a ternary (ligand-metal ion-substrate) complex; (b) within such a complex, a nucleophilic attack of the ligand hydroxyl on the substrate to give a transacylation intermediate; and (c) the metal ion promoted hydrolysis of the transacylation intermediate with a relatively fast turnover of the catalyst. Such a mode of action does not operate outside or in the absence of micellar aggregates: in this case; the hydroxyl is displaced by water that acts as the nucleophile ina slower (less enantioselective) process. The enantioselectivity of the transacylation process appears to be little affected by the steric interaction between the substituents at the chiral center of the amino acid ester and of the ligand. We suggest that the enantioselectivity arises from a different hydration, due to steric reasons, of the diastereomeric complexes comprising the two enantiomers of the substrate. As a consequence, the relevance of the competing mechanisms of cleavage of the ester, the first one, faster, involving the hydroxyl and the second one, slower, involving a Cu(II)-bound water molecule, may be different. In the case of the less hydrated, more hydrophobic R-S or S-R complex the former, faster, mode of cleavage may be more relevant than in the case of the more hydrated, less hydrophobic, S-S or R-R complex.