(R_P)-(tert-butyl)(methyl)phenylphosphine | 38736-54-8

• 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_P)-(tert-butyl)(methyl)phenylphosphine
• 英文别名: t-Butylmethylphosphin；(R)-tert-butyl-methyl-phenylphosphane
• CAS: 38736-54-8
• 化学式: C₁₁H₁₇P
• 分子量: 180.23
• InChiKey: UPXLDMOZJLPIMF-LBPRGKRZSA-N

物化性质

• 沸点：
  241.3±9.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.45
• 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：

  t-butylphenylphosphine-borane 在 三乙烯二胺 、 正丁基锂 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 反应 17.0h， 生成 (R_P)-(tert-butyl)(methyl)phenylphosphine
  参考文献：
  名称：

  Synthesis and Application of P-Stereogenic Phosphines as Superior Reagents in the Asymmetric Aza-Wittig Reaction

  摘要：

  [GRAPHICS]A wide variety of P-stereogenic aryldialkylphosphines were prepared in enantioenriched form by a systematic diversification of the (-)-sparteine-mediated dynamic kinetic resolution of racemic lithiophosphine-boranes reported by Livinghouse. Excellent asymmetric induction was observed provided that the intermediate lithiophosphine/sparteine complex precipitated from solution; more soluble derivatives returned poor ee's or racemic material. The resulting phosphine-boranes were deprotected and used as reagents in the desymmetrizing asymmetric aza-Wittig reaction of 2-alkyl-2-(3-azidopropyl)cyclohexane-1,3-diones, delivering the highest ee's yet observed in this process (up to 84% ee). Phosphines bearing bulky substituents required heating for the aza-Wittig reaction to proceed to completion, which P-31 NMR studies showed to be due to interception of the reaction by the formation of unreactive (E)-phosphazides. This was circumvented by use of methyltrioxorhenium to catalyze the formation of iminophosphoranes from the azide and phosphine, allowing reactions to take place at ambient temperature, although the ee's of the asymmetric reactions were reduced in these examples.

  DOI：

  10.1021/jo0709908

文献信息

• Effect of structure on the rate of pyramidal inversion of acyclic phosphines
  作者：Raymond D. Baechler、Kurt Mislow

  DOI：10.1021/ja00713a028

  日期：1970.5
• HORNER, L.;DICKERHOF, K., PHOSPH. AND SULFUR, 1983, 15, N 2, 213-218
  作者：HORNER, L.、DICKERHOF, K.

  DOI：——

  日期：——
• Synthesis and Application of <i>P</i>-Stereogenic Phosphines as Superior Reagents in the Asymmetric Aza-Wittig Reaction
  作者：Catherine E. Headley、Stephen P. Marsden

  DOI：10.1021/jo0709908

  日期：2007.9.1

  [GRAPHICS]A wide variety of P-stereogenic aryldialkylphosphines were prepared in enantioenriched form by a systematic diversification of the (-)-sparteine-mediated dynamic kinetic resolution of racemic lithiophosphine-boranes reported by Livinghouse. Excellent asymmetric induction was observed provided that the intermediate lithiophosphine/sparteine complex precipitated from solution; more soluble derivatives returned poor ee's or racemic material. The resulting phosphine-boranes were deprotected and used as reagents in the desymmetrizing asymmetric aza-Wittig reaction of 2-alkyl-2-(3-azidopropyl)cyclohexane-1,3-diones, delivering the highest ee's yet observed in this process (up to 84% ee). Phosphines bearing bulky substituents required heating for the aza-Wittig reaction to proceed to completion, which P-31 NMR studies showed to be due to interception of the reaction by the formation of unreactive (E)-phosphazides. This was circumvented by use of methyltrioxorhenium to catalyze the formation of iminophosphoranes from the azide and phosphine, allowing reactions to take place at ambient temperature, although the ee's of the asymmetric reactions were reduced in these examples.