(R)-1-Phenyl-2,3-dihydro-1H-phosphole

• 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: (R)-1-Phenyl-2,3-dihydro-1H-phosphole
• 英文别名: (1R)-1-phenyl-2,3-dihydrophosphole
• 化学式: C₁₀H₁₁P
• 分子量: 162.171
• InChiKey: SQPBUMZVCSANQX-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.2
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  (R)-1-Phenyl-2,3-dihydro-1H-phosphole 在 1,2,3,4,5,6,7,8-八硫杂环辛烷 、 n 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 生成 (1R,2S)-2-(Diphenyl-phosphinothioyl)-1-phenyl-phospholane 1-sulfide
  参考文献：
  名称：

  Unprecedented Inversion of Configuration at Carbon in the Electrophilic Cleavage of the Carbon-Zirconium(IV) Bond

  摘要：

  Exchange reactions between the alpha-zirconated phospholane 3, obtained by the addition of [Cp(2)ZrHCl](n) (2) to the dihydrophosphole 1, and dimethyl- or diphenylchlorophosphine 4a or 4b or bis(diisopropylamino)- or bis(dicyclohexylamino)phosphenium salts 5a or 5b, proceed with inversion of configuration at the alpha-substituted phospholane carbon atom and lead to diphosphines 6a,b,d,e. The optically active dihydrophosphole (R(p))-1 reacts with [Cp(2)ZrHCl](n) then diphenylchlorophosphine to give the 1,1-diphosphine 6b* isolated in the form of the optically active diphosphine disulfide (R(p))-14, which is characterized by X-ray diffraction studies (crystal data for (R(p))-14: orthorombic, P2(1)2(1)2(1), a = 8.391(5) Angstrom, b = 10.880(3) Angstrom, c = 22.651(6) Angstrom, R = 0.038). In contrast, retention of configuration at the alpha-substituted phospholane carbon atom in 3 is observed when 3 is reacted with the chlorodiazaphospholane 4c, giving rise to the diphosphine 6c isolated in the form of the diphosphine disulfide 15. 15 is characterized by X-ray diffraction studies (crystal data for 15: monoclinic, P2(1)/C, a = 8.243(5) Angstrom, b = 23.468(3) Angstrom, c = 9.412(6) Angstrom, R = 0.042). Comparison of the structures of 3, 6b, (R(p))-14, and 15 is done on the basis of NMR data, molecular modeling, and X-ray crystallographic studies.

  DOI：

  10.1021/ja00136a005

文献信息

• New enantiopure cyclic β-iminophosphine ligands: applications in Pd-catalyzed asymmetric allylic substitution
  作者：Maria Zablocka、Marek Koprowski、Bruno Donnadieu、Jean-Pierre Majoral、Mathieu Achard、Gérard Buono

  DOI：10.1016/s0040-4039(03)00182-5

  日期：2003.3

  New enantiopure cyclic beta-iminophosphines were applied as ligands in Pd-catalyzed asymmetric allylic substitution reactions. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Unprecedented Inversion of Configuration at Carbon in the Electrophilic Cleavage of the Carbon-Zirconium(IV) Bond
  作者：Maria Zablocka、Alain Igau、Nathalie Cenac、Bruno Donnadieu、Francoise Dahan、Jean Pierre Majoral、Michal K. Pietrusiewicz

  DOI：10.1021/ja00136a005

  日期：1995.8

  Exchange reactions between the alpha-zirconated phospholane 3, obtained by the addition of [Cp(2)ZrHCl](n) (2) to the dihydrophosphole 1, and dimethyl- or diphenylchlorophosphine 4a or 4b or bis(diisopropylamino)- or bis(dicyclohexylamino)phosphenium salts 5a or 5b, proceed with inversion of configuration at the alpha-substituted phospholane carbon atom and lead to diphosphines 6a,b,d,e. The optically active dihydrophosphole (R(p))-1 reacts with [Cp(2)ZrHCl](n) then diphenylchlorophosphine to give the 1,1-diphosphine 6b* isolated in the form of the optically active diphosphine disulfide (R(p))-14, which is characterized by X-ray diffraction studies (crystal data for (R(p))-14: orthorombic, P2(1)2(1)2(1), a = 8.391(5) Angstrom, b = 10.880(3) Angstrom, c = 22.651(6) Angstrom, R = 0.038). In contrast, retention of configuration at the alpha-substituted phospholane carbon atom in 3 is observed when 3 is reacted with the chlorodiazaphospholane 4c, giving rise to the diphosphine 6c isolated in the form of the diphosphine disulfide 15. 15 is characterized by X-ray diffraction studies (crystal data for 15: monoclinic, P2(1)/C, a = 8.243(5) Angstrom, b = 23.468(3) Angstrom, c = 9.412(6) Angstrom, R = 0.042). Comparison of the structures of 3, 6b, (R(p))-14, and 15 is done on the basis of NMR data, molecular modeling, and X-ray crystallographic studies.