N-tert-butyloxycarbonylglutathione | 137342-09-7

• 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-tert-butyloxycarbonylglutathione
• 英文别名: Boc-gGlu-Cys-Gly-OH；(2S)-5-[[(2R)-1-(carboxymethylamino)-1-oxo-3-sulfanylpropan-2-yl]amino]-2-[(2-methylpropan-2-yl)oxycarbonylamino]-5-oxopentanoic acid
• CAS: 137342-09-7
• 化学式: C₁₅H₂₅N₃O₈S
• 分子量: 407.445
• InChiKey: SGVGXZUYPSIJPZ-IUCAKERBSA-N

物化性质

• 沸点：
  782.7±60.0 °C(Predicted)
• 密度：
  1.338±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  -0.6
• 重原子数：
  27
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  172
• 氢给体数：
  6
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  N-tert-butyloxycarbonylglutathione 在 氨 、 sodium 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 1.08h， 生成
  参考文献：
  名称：

  串联质谱分析肝毒素1,1-二氯乙烯反应性代谢产物中的模型肽加合物。

  摘要：

  二氯乙烯（DCE）是一种肝毒素，它会在肝细胞中受到细胞色素P450催化的生物活化，从而形成2-氯乙酰氯和1,1-二氯环氧乙烷。2-氯乙酰氯与亲核残基和N-末端胺反应生成2-氯乙酰化残基并与谷胱甘肽反应形成反应性亲电试剂S-（2-氯乙酰基）谷胱甘肽（ClCH（2）COSG），反过来能够进行巯基烷基化。1,1-DCE氧化物可以与半胱氨酸巯基结合，随后水解形成S-羧甲基化的半胱氨酸残基。合成模型含半胱氨酸的肽的S-羧甲基化，2-氯乙酰化和GSCOCH（2）-S-Cys-肽加合物，并通过电喷雾串联质谱法对其片段化模式进行表征。GSCOCH（2）-S-Cys-肽加合物的合成是通过ClCH（2）COSG的新型叔丁氧羰基（tBOC）衍生物实现的。GSCOCH（2）-S-Cys-肽加合物的CID导致产物离子和中性损失，表明GSCOCH（2）-S-Cys部分以及b-和y-离子系列中的片段离子对对应于修饰的半

  DOI：

  10.1021/tx000148w
• 作为产物：
  描述：

  L-谷胱甘肽 (氧化型) 在 sodium hydroxide 、 三(2-羰基乙基)磷盐酸盐 、 三乙胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 1.0h， 生成 N-tert-butyloxycarbonylglutathione
  参考文献：
  名称：

  串联质谱分析肝毒素1,1-二氯乙烯反应性代谢产物中的模型肽加合物。

  摘要：

  二氯乙烯（DCE）是一种肝毒素，它会在肝细胞中受到细胞色素P450催化的生物活化，从而形成2-氯乙酰氯和1,1-二氯环氧乙烷。2-氯乙酰氯与亲核残基和N-末端胺反应生成2-氯乙酰化残基并与谷胱甘肽反应形成反应性亲电试剂S-（2-氯乙酰基）谷胱甘肽（ClCH（2）COSG），反过来能够进行巯基烷基化。1,1-DCE氧化物可以与半胱氨酸巯基结合，随后水解形成S-羧甲基化的半胱氨酸残基。合成模型含半胱氨酸的肽的S-羧甲基化，2-氯乙酰化和GSCOCH（2）-S-Cys-肽加合物，并通过电喷雾串联质谱法对其片段化模式进行表征。GSCOCH（2）-S-Cys-肽加合物的合成是通过ClCH（2）COSG的新型叔丁氧羰基（tBOC）衍生物实现的。GSCOCH（2）-S-Cys-肽加合物的CID导致产物离子和中性损失，表明GSCOCH（2）-S-Cys部分以及b-和y-离子系列中的片段离子对对应于修饰的半

  DOI：

  10.1021/tx000148w

文献信息

• Site-selective S-gem-difluoroallylation of unprotected peptides with 3,3-difluoroallyl sulfonium salts
  作者：Jin-Xiu Ren、Minqi Zhou、Xiao-Tian Feng、Hai-Yang Zhao、Xia-Ping Fu、Xingang Zhang

  DOI：10.1039/d4sc02681k

  日期：——

  Bench-stable 3,3-difluoroallyl sulfonium salts (DFASs), featuring tunable activity and their editable C-β and gem-difluoroallyl group, proved to be versatile fluoroalkylating reagents for site-selective S-gem-difluoroallylation of cysteine residues in unprotected peptides. The reaction proceeds with high efficiency under mild conditions (ambient temperature and aqueous and weak basic conditions). Various

  实验室稳定的 3,3-二氟烯丙基锍盐 (DFAS) 具有可调节的活性及其可编辑的 C-β 和 gem -二氟烯丙基基团，被证明是用于对未受保护的肽中的半胱氨酸残基进行位点选择性S-gem -二氟烯丙基化的通用氟烷基化试剂。该反应在温和条件（环境温度、水相和弱碱性条件）下高效进行。各种受保护/未受保护的肽，尤其是生物活性肽，被位点选择性地S-gem-二氟烯丙基化。新添加的偕二氟烯丙基和源自 DFAS 的 C-β 的其他官能团准备通过点击和自由基化学与生物官能团连接。这种肽的逐步“双正交”修饰使得能够构建具有增强的复杂性和功能性的生物缀合物。这一原理证明已成功应用于构建肽-糖-生物素嵌合生物缀合物，表明其在药物化学和化学生物学中的巨大应用潜力。
• Synthesis, Characterization, and Solvolysis of Mono- and Bis-<i>S</i>-(glutathionyl) Adducts of Methylene-bis-(phenylisocyanate) (MDI)
  作者：Martin Reisser、Brigitte F. Schmidt、William E. Brown

  DOI：10.1021/tx0255020

  日期：2002.10.1

  Bifunctional isocyanates are highly reactive compounds that undergo nucleophilic attack by a variety of functional groups available in the biological system. While the etiology of the respiratory disease caused by diisocyanates is not fully understood, a great deal of research has been performed to elucidate the chemical mechanisms involved in the direct and indirect effects of these compounds. Since adducts of isocyanates are found not only to proteins along the entire respiratory tree but also to proteins in the circulatory system, it is likely that a transport mechanism for the isocyanate from the respiratory to the circulatory system exists. The initial reaction of isocyanates with cellular thiols to form thiocarbamates, which are known to release the isocyanate under physiological conditions, is believed to provide a possible carrier mechanism for the isocyanate functional group. Previous work with aliphatic mono-isocyanates and the aromatic diisocyanate toluene diisocyanate has demonstrated the feasibility of this mechanisin. Adding to this database, the products of the reaction of the highly water-insoluble, low vapor pressure, methylene-bis-(phenylisocyanate) (MDI) with glutathione were synthesized, and their chemical stability under various pH and buffer conditions was tested. Novel synthetic routes were developed for both the mono- and bis-S-(glutathionyl) adducts with MDI that yielded each compound in analytically pure form. Both compounds were found to be unstable under mild basic conditions (phosphate-buffered saline, pH 7.4, and NaHCO3, pH 8.2), however to a different degree. Furthermore, a significant influence of the pH value (the rate of degradation increases with pH) and the concentration of free glutathione (increasing thiol stabilizes the adduct) on the stability was observed, indicating a base-catalyzed mechanism of the degradation/formation of the thiocarbamate bond. Unlike the monoadduct, which forms almost exclusively the polyurea upon degradation, a variety of products were formed upon degradation of the his adduct. Though the disappearance of the his adduct was complete as measured by HPLC, H-1 NMR spectra showed the existence of residual thiocarbamate bonds in the final mixture. In both cases, no evidence of the free methylene-bis-phenylamine (MDA) could be detected under the applicable conditions.