(S)-2-((S,E)-5-(bis(tert-butoxycarbonyl)amino)-6-methoxy-6-oxohex-1-enyl)pentanedioic acid | 1100130-90-2

• 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: (S)-2-((S,E)-5-(bis(tert-butoxycarbonyl)amino)-6-methoxy-6-oxohex-1-enyl)pentanedioic acid
• 英文别名: (2S)-2-[(E,5S)-5-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]-6-methoxy-6-oxohex-1-enyl]pentanedioic acid
• CAS: 1100130-90-2
• 化学式: C₂₂H₃₅NO₁₀
• 分子量: 473.521
• InChiKey: IPROJVBBNNUYEO-SUMGSTKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  33
• 可旋转键数：
  15
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.68
• 拓扑面积：
  157
• 氢给体数：
  2
• 氢受体数：
  10

反应信息

• 作为反应物：
  描述：

  (S)-2-((S,E)-5-(bis(tert-butoxycarbonyl)amino)-6-methoxy-6-oxohex-1-enyl)pentanedioic acid 、 三甲基硅烷化重氮甲烷 在 甲醇 作用下， 反应 16.0h， 以85%的产率得到trimethyl (E,3S,8S)-8-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]oct-4-ene-1,3,8-tricarboxylate
  参考文献：
  名称：

  Synthesis of Isopeptide Epoxide Peptidomimetics

  摘要：

  Two epoxide-containing peptidomimetics of the isopeptide, glutatnyl-gamma-glutamate, have been synthesized via a route that should be generally applicable to the synthesis of isopeptide analogues in which an oxirane replaces the scissile peptide bond. Enzymes that catalyze the hydrolysis of peptides and isopeptides are often susceptible to inactivation by electrophilic substrate analogues. In this research, an epoxide was installed as an electrophilic replacement of the scissile isopeptide bond. The C-terminal glutamyl mimic was accessed by the stereospecific synthesis of suitably substituted cyclopentenes, 8 and 10, as surrogates for either the L- or D- enantiomer. The enantiomeric cyclopentenes were further elaborated to incorporate an appended sulfone that was reacted with a suitably protected glutamyl-gamma-semialdehyde in a Julia-Kocienski olefination reaction. This olefination afforded predominantly the desired E-olefin isosteres of L-glutamyl-gamma-D-glutamate and L-glutamyl-gamma-L-glutamate, following which peracid-mediated epoxidation and deprotection provided the epoxide-containing peptidomimetics, 4 and 5.

  DOI：

  10.1021/jo801907p
• 作为产物：
  描述：

  methyl (E,2S,7S)-2-[bis[(2-methylpropan-2-yl)oxycarbonyl]amino]-7-formyl-10-oxodec-5-enoate 在 sodium chlorite 、 sodium dihydrogenphosphate 、 2-甲基-2-丁烯 、 水 作用下， 以 四氢呋喃 、 叔丁醇 为溶剂， 反应 3.0h， 生成 (S)-2-((S,E)-5-(bis(tert-butoxycarbonyl)amino)-6-methoxy-6-oxohex-1-enyl)pentanedioic acid
  参考文献：
  名称：

  Synthesis of Isopeptide Epoxide Peptidomimetics

  摘要：

  Two epoxide-containing peptidomimetics of the isopeptide, glutatnyl-gamma-glutamate, have been synthesized via a route that should be generally applicable to the synthesis of isopeptide analogues in which an oxirane replaces the scissile peptide bond. Enzymes that catalyze the hydrolysis of peptides and isopeptides are often susceptible to inactivation by electrophilic substrate analogues. In this research, an epoxide was installed as an electrophilic replacement of the scissile isopeptide bond. The C-terminal glutamyl mimic was accessed by the stereospecific synthesis of suitably substituted cyclopentenes, 8 and 10, as surrogates for either the L- or D- enantiomer. The enantiomeric cyclopentenes were further elaborated to incorporate an appended sulfone that was reacted with a suitably protected glutamyl-gamma-semialdehyde in a Julia-Kocienski olefination reaction. This olefination afforded predominantly the desired E-olefin isosteres of L-glutamyl-gamma-D-glutamate and L-glutamyl-gamma-L-glutamate, following which peracid-mediated epoxidation and deprotection provided the epoxide-containing peptidomimetics, 4 and 5.

  DOI：

  10.1021/jo801907p

文献信息

• Synthesis of Isopeptide Epoxide Peptidomimetics
  作者：Debatosh Majumdar、Matthew D. Alexander、James K. Coward

  DOI：10.1021/jo801907p

  日期：2009.1.16

  Two epoxide-containing peptidomimetics of the isopeptide, glutatnyl-gamma-glutamate, have been synthesized via a route that should be generally applicable to the synthesis of isopeptide analogues in which an oxirane replaces the scissile peptide bond. Enzymes that catalyze the hydrolysis of peptides and isopeptides are often susceptible to inactivation by electrophilic substrate analogues. In this research, an epoxide was installed as an electrophilic replacement of the scissile isopeptide bond. The C-terminal glutamyl mimic was accessed by the stereospecific synthesis of suitably substituted cyclopentenes, 8 and 10, as surrogates for either the L- or D- enantiomer. The enantiomeric cyclopentenes were further elaborated to incorporate an appended sulfone that was reacted with a suitably protected glutamyl-gamma-semialdehyde in a Julia-Kocienski olefination reaction. This olefination afforded predominantly the desired E-olefin isosteres of L-glutamyl-gamma-D-glutamate and L-glutamyl-gamma-L-glutamate, following which peracid-mediated epoxidation and deprotection provided the epoxide-containing peptidomimetics, 4 and 5.