2-(diphenylphosphanyl)benzoic acid isopropyl ester | 628708-20-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 2-(diphenylphosphanyl)benzoic acid isopropyl ester
• 英文别名: Propan-2-yl 2-diphenylphosphanylbenzoate
• CAS: 628708-20-3
• 化学式: C₂₂H₂₁O₂P
• 分子量: 348.381
• InChiKey: PRESDKNMZJPMLL-UHFFFAOYSA-N

物化性质

• 沸点：
  453.4±28.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  苄基叠氮 、 2-(diphenylphosphanyl)benzoic acid isopropyl ester 在 水 作用下， 以 氘代乙腈 为溶剂， 生成 diphenylphosphine oxide
  参考文献：
  名称：

  Mechanistic Investigation of the Staudinger Ligation

  摘要：

  The Staudinger ligation of azides and phosphines has found widespread use in the field of chemical biology, but the mechanism of the transformation has not been characterized in detail. In this work, we undertook a mechanistic study of the Staudinger ligation with a focus on factors that affect reaction kinetics and on the identification of intermediates. The Staudinger ligation with alkyl azides was second-order overall and proceeded more rapidly in polar, protic solvents. Hammett analyses demonstrated that electron-donating substituents on the phosphine accelerate the overall reaction. The electronic and steric properties of the ester had no significant impact on the overall rate but did affect product ratios. Finally, the structure of an intermediate that accumulates under anhydrous conditions was identified. These findings establish a platform for optimizing the Staudinger ligation for expanded use in biological applications.

  DOI：

  10.1021/ja044461m
• 作为产物：
  描述：

  二苯基膦 、 isopropyl 2-iodobenzoate 在 palladium diacetate 、 1,3-双(二苯基膦)丙烷 、 三乙胺 作用下， 以 乙腈 为溶剂， 以37%的产率得到2-(diphenylphosphanyl)benzoic acid isopropyl ester
  参考文献：
  名称：

  Mechanistic Investigation of the Staudinger Ligation

  摘要：

  The Staudinger ligation of azides and phosphines has found widespread use in the field of chemical biology, but the mechanism of the transformation has not been characterized in detail. In this work, we undertook a mechanistic study of the Staudinger ligation with a focus on factors that affect reaction kinetics and on the identification of intermediates. The Staudinger ligation with alkyl azides was second-order overall and proceeded more rapidly in polar, protic solvents. Hammett analyses demonstrated that electron-donating substituents on the phosphine accelerate the overall reaction. The electronic and steric properties of the ester had no significant impact on the overall rate but did affect product ratios. Finally, the structure of an intermediate that accumulates under anhydrous conditions was identified. These findings establish a platform for optimizing the Staudinger ligation for expanded use in biological applications.

  DOI：

  10.1021/ja044461m

文献信息

• Conversion of Aryl Azides to <i>O</i>-Alkyl Imidates via Modified Staudinger Ligation
  作者：José A. Restituyo、Lindsay R. Comstock、Scott G. Petersen、Thomas Stringfellow、Scott R. Rajski

  DOI：10.1021/ol035635s

  日期：2003.11.1

  o-Carboalkoxy triarylphosphines are shown to react with aryl azides to provide Staudinger ligation products bearing O-alkyl imidate linkages. This is in contrast to alkyl azides whose ligation to o-carboalkoxy triarylphosphines has been reported to yield amide-linked materials. This extension of the Staudinger ligation for coupling of abiotic reagents under biocompatible conditions highlights the utility of commercially available triarylphosphines through which suitable linkers can be attached via an ester moiety.