S-[bis(4-methoxyphenyl)phosphanylmethyl] (2S)-2-acetamidopropanethioate | 922517-74-6

• 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-[bis(4-methoxyphenyl)phosphanylmethyl] (2S)-2-acetamidopropanethioate
• CAS: 922517-74-6
• 化学式: C₂₀H₂₄NO₄PS
• 分子量: 405.455
• InChiKey: JIBATGJKANDFGV-AWEZNQCLSA-N

物化性质

• 沸点：
  564.5±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  27
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 拓扑面积：
  89.9
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [2-¹³C]-(2S)-2-azido-N-benzyl-1-propionamide 、 S-[bis(4-methoxyphenyl)phosphanylmethyl] (2S)-2-acetamidopropanethioate 以 1,4-二氧六环 为溶剂， 以82%的产率得到(2S)-2-acetamido-N-[(2S)-1-(benzylamino)-1-oxo(213C)propan-2-yl]propanamide
  参考文献：
  名称：

  Staudinger Ligation of Peptides at Non-Glycyl Residues

  摘要：

  The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino) methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino) methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.

  DOI：

  10.1021/jo0620056
• 作为产物：
  描述：

  Thioacetic acid S-[bis-(4-methoxy-phenyl)-phosphinoylmethyl] ester 在 sodium hydroxide 、 三氯硅烷 、 1-羟基苯并三唑 、 N,N'-二环己基碳二亚胺 作用下， 以 甲醇 、 氯仿 、 N,N-二甲基甲酰胺 为溶剂， 反应 77.5h， 生成 S-[bis(4-methoxyphenyl)phosphanylmethyl] (2S)-2-acetamidopropanethioate
  参考文献：
  名称：

  Staudinger Ligation of Peptides at Non-Glycyl Residues

  摘要：

  The Staudinger ligation provides a means to form an amide bond between a phosphinothioester and azide. This reaction holds promise for the ligation of peptides en route to the total chemical synthesis of proteins. (Diphenylphosphino) methanethiol is the most efficacious of known reagents for mediating the Staudinger ligation of peptides, providing high (> 90%) isolated yields for equimolar couplings in which a glycine residue is at the nascent junction. Surprisingly, the yields are lower (< 50%) for non-glycyl couplings due to an aza-Wittig reaction that diverts the reaction toward a phosphonamide byproduct. Here, the partitioning of the reaction toward Staudinger ligation (and away from the aza-Wittig reaction) is shown to increase with increasing electron density on phosphorus. This electron density can be tuned either by installing functional groups on the phenyl substituents of (diphenylphosphino) methanethiol or by changing the polarity of the solvent. Installing p-methoxy groups and using a solvent of low polarity (such as toluene or dioxane) provide especially high (> 80%) isolated yields for the ligation of two non-glycyl residues. These conditions retain the high chemoselectivity of the reaction and do not lead to a substantial change in reaction rate. The traceless Staudinger ligation is now poised to enable the iterative ligation of peptides with little regard for their sequence, as well as the synthesis of amide bonds for other purposes.

  DOI：

  10.1021/jo0620056

文献信息

• Electronic and steric effects on the rate of the traceless Staudinger ligation
  作者：Annie Tam、Matthew B. Soellner、Ronald T. Raines

  DOI：10.1039/b802336k

  日期：——

  Interplay between electronic effects imparted by phosphinothiol substituents and steric effects imposed by amino-acid reactants affects the rate of the traceless Staudinger ligation of peptides in a predictable manner.

  膦硫醇取代基赋予的电子效应与氨基酸反应物施加的空间效应之间的相互作用以可预测的方式影响肽的无痕 Staudinger 连接速率。