3-chloro-4-diphenylhydroxymethyl-5-phenyl-5H-dibenzophosphole 5-oxide

• 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: 3-chloro-4-diphenylhydroxymethyl-5-phenyl-5H-dibenzophosphole 5-oxide
• 英文别名: (3-Chloro-5-oxo-5-phenylbenzo[b]phosphindol-4-yl)-diphenylmethanol；(3-chloro-5-oxo-5-phenylbenzo[b]phosphindol-4-yl)-diphenylmethanol
• 化学式: C₃₁H₂₂ClO₂P
• 分子量: 492.941
• InChiKey: KGEIKFUOFFKLGT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.7
• 重原子数：
  35
• 可旋转键数：
  4
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.03
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  5-phenyl-5H-dibenzophosphole-5-oxide 在 2,2,6,6-tetramethylpiperidinyl-lithium 、 异丙基氯化镁 、 一氯化碘 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 0.33h， 生成 3-chloro-4-diphenylhydroxymethyl-5-phenyl-5H-dibenzophosphole 5-oxide
  参考文献：
  名称：

  Rigid P-chiral mono and diphosphines. Configurative stability and P-inversion barrier

  摘要：

  A group of P-chiral monophosphine oxides and one diaryl diphosphine oxide based on the dibenzophosphole skeleton have been synthesized. Preparative enantioselective chromatography of 4-trimethylsilyl-5-phenyl-5H-dibenzophosphol oxide followed by a simple transformation with exchange of substituents (and a homo-coupling reaction in one case) and a stereoselective reduction step furnished the corresponding phosphines in fair to good yield. Their relative and absolute configurations were determined by crystal structure analysis. It turned out that racemization of the phosphines through P-inversion takes place at ambient temperature and depends markedly on ortho substituents (104-114 kJ mol(-1)). In the case of the diphosphine, racemization can be suppressed when forming a chelate with Pd(II) or Ni(II) complexes. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2006.05.005

文献信息

• Rigid P-chiral mono and diphosphines. Configurative stability and P-inversion barrier
  作者：Michael Widhalm、Lothar Brecker、Kurt Mereiter

  DOI：10.1016/j.tetasy.2006.05.005

  日期：2006.5

  A group of P-chiral monophosphine oxides and one diaryl diphosphine oxide based on the dibenzophosphole skeleton have been synthesized. Preparative enantioselective chromatography of 4-trimethylsilyl-5-phenyl-5H-dibenzophosphol oxide followed by a simple transformation with exchange of substituents (and a homo-coupling reaction in one case) and a stereoselective reduction step furnished the corresponding phosphines in fair to good yield. Their relative and absolute configurations were determined by crystal structure analysis. It turned out that racemization of the phosphines through P-inversion takes place at ambient temperature and depends markedly on ortho substituents (104-114 kJ mol(-1)). In the case of the diphosphine, racemization can be suppressed when forming a chelate with Pd(II) or Ni(II) complexes. (c) 2006 Elsevier Ltd. All rights reserved.