1H-2,3-diphenylphosphindole | 919766-04-4

• 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: 1H-2,3-diphenylphosphindole
• 英文别名: 2,3-diphenyl-1H-phosphindole
• CAS: 919766-04-4
• 化学式: C₂₀H₁₅P
• 分子量: 286.313
• InChiKey: WOBQMCNOOMWADT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  21
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为产物：
  描述：

  alkaline earth salt of/the/ methylsulfuric acid 以 二氯甲烷 为溶剂， 以100%的产率得到1H-2,3-diphenylphosphindole
  参考文献：
  名称：

  A Synthetic Cycle for the Ruthenium-Promoted Formation of 1H-Phosphindoles from Phosphaalkynes

  摘要：

  Beginning with inexpensive and commercially available starting materials, a rational synthesis for the new phosphaalkyne Ph3C-C P ( 1) is presented. Coordination of 1 to group 8 transition metal centers furnishes the eta(1)-complexes [ MH( dppe)(2)( Ph3CC P)] OTf, where M) Fe ( 3) or Ru ( 4) ( dppe) bis-1,2-diphenylphosphinoethane). Treatment of 3 or 4 with a strong acid cyclizes the coordinated phosphaalkyne and is the first example of an electrophilic aromatic substitution reaction in which the electrophile is a low coordinate phosphorus. With the aid of DFT calculations, we were able to gain a more thorough understanding of the energetics and mechanism of this new cyclization reaction. Thermolysis of the iron-3,3-diphenyl-3H-phosphindole adduct ( 6) in CH3CN results in quantitative formation of the free 3H-phosphindole ( 7). Alternatively, when ruthenium-3,3-diphenyl-3H-phosphindole adduct ( 5) is irradiated, a photochemical rearrangement occurs furnishing 2,3-diphenyl-1H-phosphindole ( 9). Mechanistic work is presented that provides an explanation for this transformation. Compounds 1, 3, 5, and 9 have been characterized by single X-ray diffraction studies. Finally, a synthetic cycle for the conversion of 1 to 1H-phosphindole 9 has been developed that recycles the ruthenium cation [ RuH( dppe)(2)](+).

  DOI：

  10.1021/ja0651198

文献信息

• Nouveaux dérivés de la céphalosporine et leur préparation
  申请人：RHONE-POULENC SANTE

  公开号：EP0072756A1

  公开（公告）日：1983-02-23

  Nouveaux dérivés de la céphalosporine de formule générale (1) dans laquelle R' représente un radical carboxy protégé, Hal représente un atome d'halogène, X, représente un atome de soufre ou d'oxygène ou un radical sulfinyle et R représente un radical acyle ou un protecteur d'amine. Ces nouveaux produits sont utilisables comme intermédiaires pour la préparation de médicaments antibactériens du groupe des céphalosporines.

  式中的新头孢菌素衍生物 (1) 式中 R' 代表受保护的羧基 Hal 代表卤素原子 X 代表硫或氧原子或亚磺酰基，R 代表酰基或胺保护基。 这些新产品可用作制备头孢菌素类抗菌药物的中间体。
• A Synthetic Cycle for the Ruthenium-Promoted Formation of 1<i>H</i>-Phosphindoles from Phosphaalkynes
  作者：Joseph G. Cordaro、Daniel Stein、Hansjörg Grützmacher

  DOI：10.1021/ja0651198

  日期：2006.11.1

  Beginning with inexpensive and commercially available starting materials, a rational synthesis for the new phosphaalkyne Ph3C-C P ( 1) is presented. Coordination of 1 to group 8 transition metal centers furnishes the eta(1)-complexes [ MH( dppe)(2)( Ph3CC P)] OTf, where M) Fe ( 3) or Ru ( 4) ( dppe) bis-1,2-diphenylphosphinoethane). Treatment of 3 or 4 with a strong acid cyclizes the coordinated phosphaalkyne and is the first example of an electrophilic aromatic substitution reaction in which the electrophile is a low coordinate phosphorus. With the aid of DFT calculations, we were able to gain a more thorough understanding of the energetics and mechanism of this new cyclization reaction. Thermolysis of the iron-3,3-diphenyl-3H-phosphindole adduct ( 6) in CH3CN results in quantitative formation of the free 3H-phosphindole ( 7). Alternatively, when ruthenium-3,3-diphenyl-3H-phosphindole adduct ( 5) is irradiated, a photochemical rearrangement occurs furnishing 2,3-diphenyl-1H-phosphindole ( 9). Mechanistic work is presented that provides an explanation for this transformation. Compounds 1, 3, 5, and 9 have been characterized by single X-ray diffraction studies. Finally, a synthetic cycle for the conversion of 1 to 1H-phosphindole 9 has been developed that recycles the ruthenium cation [ RuH( dppe)(2)](+).