N-methyloxycarbonyl-D-leucyl-L-alanyl-L-alanine methyl ester | 1235348-04-5

• 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-methyloxycarbonyl-D-leucyl-L-alanyl-L-alanine methyl ester
• 英文别名: Moc-D-Leu-L-Ala-L-Ala-OMe；MeOCO-D-Leu-Ala-Ala-OMe；methyl (2S)-2-[[(2S)-2-[[(2R)-2-(methoxycarbonylamino)-4-methylpentanoyl]amino]propanoyl]amino]propanoate
• CAS: 1235348-04-5
• 化学式: C₁₅H₂₇N₃O₆
• 分子量: 345.396
• InChiKey: VWGCRDMUDAMHSU-GARJFASQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  24
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  123
• 氢给体数：
  3
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  N-methyloxycarbonyl-D-leucyl-L-alanyl-L-alanine methyl ester 在 甲基(三氟甲基)-1,3-二环氧丙烷 作用下， 以 1,1,1-三氟丙酮 、 丙酮 为溶剂， 生成 N-(4-methyl-2-nitropentanoyl)-L-alanyl-L-alanine methyl ester 、 N-(4-methyl-2-nitropentanoyl)-L-alanyl-L-alanine methyl ester 、 N-methyloxycarbonyl-N-hydroxy-D-leucyl-L-alanyl-L-alanine methyl ester 、 N-methyloxycarbonyl-γ-hydroxy-D-leucyl-L-alanyl-L-alanine methyl ester
  参考文献：
  名称：

  Concerning Selectivity in the Oxidation of Peptides by Dioxiranes. Further Insight into the Effect of Carbamate Protecting Groups

  摘要：

  With use of methyl(trifluoromethyl)dioxirane (TFDO), the oxidation of some tripeptide esters protected at the N-terminus with carbamate or amide groups could be achieved efficiently under mild conditions with no loss of configuration at the chiral centers. Expanding on preliminary investigations, it is found that, while peptides protected with amide groups (PG = Ac-, Tfa-, Piv-) undergo exclusive hydroxylation at the side chain, their analogues bearing a carbamate group (PG = Cbz-, Moc-, Boc-, TcBoc-) give competitive and/or concurrent hydroxylation at the terminal N-H moiety. Valuable nitro derivatives are also formed as a result of oxidative deprotection of the carbamate group with excess dioxirane. A rationale is proposed to explain the dependence of the selectivity upon the nature of the protecting group.

  DOI：

  10.1021/jo100855h
• 作为产物：
  描述：

  N-tert-butyloxycarbonyl-D-leucyl-L-alanyl-L-alanine methyl ester 、 氯甲酸甲酯 在 三氟乙酸 、 吡啶 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到N-methyloxycarbonyl-D-leucyl-L-alanyl-L-alanine methyl ester
  参考文献：
  名称：

  Concerning Selectivity in the Oxidation of Peptides by Dioxiranes. Further Insight into the Effect of Carbamate Protecting Groups

  摘要：

  With use of methyl(trifluoromethyl)dioxirane (TFDO), the oxidation of some tripeptide esters protected at the N-terminus with carbamate or amide groups could be achieved efficiently under mild conditions with no loss of configuration at the chiral centers. Expanding on preliminary investigations, it is found that, while peptides protected with amide groups (PG = Ac-, Tfa-, Piv-) undergo exclusive hydroxylation at the side chain, their analogues bearing a carbamate group (PG = Cbz-, Moc-, Boc-, TcBoc-) give competitive and/or concurrent hydroxylation at the terminal N-H moiety. Valuable nitro derivatives are also formed as a result of oxidative deprotection of the carbamate group with excess dioxirane. A rationale is proposed to explain the dependence of the selectivity upon the nature of the protecting group.

  DOI：

  10.1021/jo100855h

文献信息

• Concerning Selectivity in the Oxidation of Peptides by Dioxiranes. Further Insight into the Effect of Carbamate Protecting Groups
  作者：Cosimo Annese、Lucia D’Accolti、Marta De Zotti、Caterina Fusco、Claudio Toniolo、Paul G. Williard、Ruggero Curci

  DOI：10.1021/jo100855h

  日期：2010.7.16

  With use of methyl(trifluoromethyl)dioxirane (TFDO), the oxidation of some tripeptide esters protected at the N-terminus with carbamate or amide groups could be achieved efficiently under mild conditions with no loss of configuration at the chiral centers. Expanding on preliminary investigations, it is found that, while peptides protected with amide groups (PG = Ac-, Tfa-, Piv-) undergo exclusive hydroxylation at the side chain, their analogues bearing a carbamate group (PG = Cbz-, Moc-, Boc-, TcBoc-) give competitive and/or concurrent hydroxylation at the terminal N-H moiety. Valuable nitro derivatives are also formed as a result of oxidative deprotection of the carbamate group with excess dioxirane. A rationale is proposed to explain the dependence of the selectivity upon the nature of the protecting group.