(R_P)-allyl(tert-butyl)(phenyl)phosphine borane | 568600-61-3

• 英文名称: (R_P)-allyl(tert-butyl)(phenyl)phosphine borane
• 英文别名: (R)-(+)-allyl(tert-butyl)phenylphosphine borane；(S_P)-allyl(tert-butyl)(phenyl)phosphine borane；(S)-allyl(tert-butyl)phenylphosphine borane
• CAS: 568600-61-3
• 化学式: C₁₃H₂₂BP
• 分子量: 220.102
• InChiKey: PEADMYNZYTYHEZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.59
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为产物：
  描述：

  tert-Butylphenylphosphine oxide 在 sodium tetrahydroborate 、 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 正己烷 、 二氯甲烷 为溶剂， 反应 4.33h， 生成 t-butylallylphenylphosphine borane 、 (R_P)-allyl(tert-butyl)(phenyl)phosphine borane
  参考文献：
  名称：

  Bulky, Optically Active P-Stereogenic Phosphine–Boranes from Pure H-Menthylphosphinates

  摘要：

  The transformation of readily available pure-H-menthylphosphinates into chiral phosphinous acid-boranes permits the elaboration of bulky P-stereogenic secondary phosphine-boranes. Taking advantage of the synthetic potential of these compounds, a broad range of hindered P-chiral tertiary phosphine-boranes has been prepared with excellent enantiomeric excesses. The utility of bulky o-tolylphosphines was illustrated by the synthesis of a rare enantiopure phosphapalladacycle (S-P,S-P)-12.

  DOI：

  10.1021/ja2034816

文献信息

• Reactivity of allyl anions of allylphosphine-boranes towards electrophiles
  作者：Marek Stankevic、Kazimierz Michał Pietrusiewicz、Marcin Siek

  DOI：10.3998/ark.5550190.0012.511

  日期：——

  The reactivity of mesomeric carbanions derived from allylphosphine-boranes varies as a function of electrophile. Small sp 3 -electrophiles react predominantly at the carbon atom whereas bulky sp 3 -electrophiles and carbonyl compounds react mainly at the carbon. In the case of electrondeficient aldehydes reduction of carbonyl group and formation of the corresponding alcohols is observed. This is attributed

  衍生自烯丙基膦-硼烷的中间体碳负离子的反应性随亲电子试剂的不同而变化。小的 sp 3 -亲电试剂主要在碳原子上反应，而大的 sp 3 -亲电试剂和羰基化合物主要在碳原子上反应。在缺电子醛的情况下，观察到羰基的还原和相应醇的形成。这归因于衍生自烯丙基膦-硼烷的碳负离子的弱还原特性，其内消旋形式类似于改性硼氢化物的结构。
• Alkylation of Phosphine Boranes by Phase-Transfer Catalysis
  作者：Hélène Lebel、Sébastien Morin、Valérie Paquet

  DOI：10.1021/ol0347139

  日期：2003.6.1

  [GRAPHICS]The alkylation of phosphine boranes with various electrophiles proceeds with good to excellent yields in a biphasic solution in the presence of tetrabutylammonium bromide as a phase-transfer catalyst.
• The Hydroxyalkyl Moiety As a Protecting Group for the Stereospecific Alkylation of Masked Secondary Phosphine-Boranes
  作者：Sébastien Lemouzy、Marion Jean、Laurent Giordano、Damien Hérault、Gérard Buono

  DOI：10.1021/acs.orglett.5b03450

  日期：2016.1.4

  The synthesis of functionalized tertiary phosphine-boranes has been developed via a chemodivergent approach from readily accessible (hydroxymethyl) phosphine-boranes under mild conditions. O-Alkylation or decarbonylative P-alkylation product could be exclusively obtained. The P-alkylation reaction was found to proceed in moderate to very good yields and very high enantiospecificity (es >95%) using a variety of alkyl halides as electrophiles. The configurational stability of the sodium phosphido-borane intermediate was also investigated and allowed a deeper understanding of the reaction mechanism, furnishing secondary phosphine-boranes in moderate yield and enantiopurity.