t-butylphenylphosphine-borane

• 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: t-butylphenylphosphine-borane
• 英文别名: (+/-)-tert-butylphenylphosphine borane；borane;tert-butyl(phenyl)phosphane
• 化学式: BH₃*C₁₀H₁₅P
• 分子量: 180.038
• InChiKey: CGDQPPNTODDNJT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.61
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  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
• 作为产物：
  描述：

  叔丁基苯基膦 在 硼烷四氢呋喃络合物 作用下， 以59%的产率得到t-butylphenylphosphine-borane
  参考文献：
  名称：

  用于开发 SUPRAPhos 配体库的构件的合成及其在催化中的应用实例

  摘要：

  我们之前已经介绍了 SUPRAPhos 配体库，它基于通过氮-锌相互作用自组装的组件，并在此报告了该库的扩展，它扩大了在不对称均相催化中的应用范围。例如，我们报告了磷酰胺附加卟啉和在磷上具有立体中心的结构单元的合成。使用本文中描述的新构建块，我们可以形成一个 450 成员的 SUPRAPhos 库，该库基于 45 个构建块（30 个吡啶基磷配体和 15 个互补的卟啉附加磷配体）。包括在铑催化的苯乙烯不对称加氢甲酰化中使用库成员的实例。

  DOI：

  10.1002/ejoc.200800499

文献信息

• Reactivity of chiral oxazaphospholidines on activated halide compounds: Synthesis and coordination studies of chiral hybrid phosphine-phosphine oxide ligands
  作者：Bruno Faure、Olivier Pardigon、Gérard Buono

  DOI：10.1016/s0040-4020(97)00749-7

  日期：1997.8

  and a mixture of diastereomers 6:7 as the Perkow products. New hybrid phosphine-phosphine oxide ligands were easily obtained from phosphinamides 3, bearing chirality on the carbon chain and the phosphine oxide moiety (BPPO), or on the carbon chain and the two different phosphorus centers (8 and 9). The coordination chemistry of ligand BPPO has been studied, with transition metals and Lewis Acids.

  对映体纯2-苯基-1,3,2-氧杂磷腈1与不同的活化卤化物化合物2之间的Michaelis Arbuzov反应提供了总的非对映选择性手性次膦酰胺3。Oxazaphospholidine 1与α-卤代苯乙酮4a-c反应，生成手性Michaelis Arbuzov产物5和非对映异构体6：7的混合物，作为Perkow产物。很容易从次膦酰胺3中获得新的杂化膦-膦氧化物配体，它们在碳链和氧化膦部分（BPPO）上或在碳链和两个不同的磷中心上具有手性（8和9）。已经研究了配体BPPO与过渡金属和路易斯酸的配位化学。
• An Expedient Reduction of<i>sec</i>-Phosphine Oxides to<i>sec</i>-Phosphine-boranesby BH₃˙SMe₂
  作者：K. Michał Pietrusiewicz、Marek Stankevič

  DOI：10.1055/s-2003-39304

  日期：——

  Secondary phosphine oxides can be expeditiously converted into secondary phosphine-boranes by treatment with an excess of BH3˙SMe2 at room temperature. Selectivity of the conversion towards the formation of secondary phosphine-boranes is greatly improved by the addition of a small amount of water to the reaction mixture.

  次级磷氧化物可以通过在室温下用过量的BH3·SMe2处理迅速转化为次级磷硼烷。向反应混合物中加入少量水可以显著提高生成次级磷硼烷的转化选择性。
• Regio- and Stereoselective Hydrophosphination Reactions of Alkynes with Phosphine−Boranes:  Access to Stereodefined Vinylphosphine Derivatives
  作者：David Mimeau、Annie-Claude Gaumont

  DOI：10.1021/jo030096q

  日期：2003.9.1

  Vinylphosphine-borane complexes are easily synthesized by regio- and stereoselective hydrophosphination of terminal alkynes with use of secondary phosphine-boranes as hydrophosphinating agent. The regioselectivity of the reaction is efficiently controlled by the choice of the activation process: thermal or metal catalyst activation. The vinylphosphine derivatives are purified by chromatography on silica

  乙烯基膦-硼烷配合物可通过使用仲膦-硼烷作为氢膦化剂，通过末端炔的区域和立体选择性加氢磷酸化而容易地合成。通过选择活化过程可以有效控制反应的区域选择性：热或金属催化剂活化。通过硅胶色谱法纯化乙烯基膦衍生物。该过程的可扩展性以克为单位进行了证明。这种简单的方法应该促进使用乙烯基膦作为有机和有机金属化学的基础。
• The Synthesis and Reactivity of Phosphinous Acid-Boranes
  作者：K. Michał Pietrusiewicz、Marek Stankevič

  DOI：10.1055/s-2005-861878

  日期：——

  Phosphinic acid chlorides are converted directly into phosphinous acid-boranes in a process utilizing BH 3 .THF complex as a reducing agent. The process is general and affords phosphinous acid-boranes in good to very high yields. Phosphinous acid-boranes have been found to react readily with alkylating, acylating, reducing, halogenating and deborating agents to produce the corresponding phosphinous acid-borane

  在使用 BH 3 .THF 络合物作为还原剂的过程中，次膦酰氯直接转化为次膦酸-硼烷。该方法是通用的并且以良好至非常高的产率提供次膦酸-硼烷。已发现次膦酸-硼烷容易与烷基化剂、酰化剂、还原剂、卤化剂和脱硼剂反应生成相应的次膦酸-硼烷酯、次膦酸-硼酸酐、仲氧化膦、仲膦硼烷和次膦酰卤， 分别。已经制定了这些转换的有效程序，并概述了它们的范围。
• Palladium-Catalyzed C−P Coupling Reactions between Vinyl Triflates and Phosphine−Boranes:  Efficient Access to Vinylphosphine−Boranes
  作者：Delphine Julienne、Jean-François Lohier、Olivier Delacroix、Annie-Claude Gaumont

  DOI：10.1021/jo062482o

  日期：2007.3.1

  complexes are easily synthesized by palladium-catalyzed C−P cross-coupling of vinyl triflates with secondary phosphine−boranes. This method allows the synthesis of phosphine derivatives not always easily accessible by other approaches. The vinylphosphine derivatives are purified by chromatography on silica gel. The versatility of the method is proved by using various triflates and diaryl-, dialkyl- and al

  乙烯基膦-硼烷络合物很容易通过钯催化的乙烯基三氟甲磺酸酯与仲膦-硼烷的CP交叉偶联而合成。该方法使得膦衍生物的合成并非总是可以通过其他方法容易地获得。通过硅胶色谱法纯化乙烯基膦衍生物。通过使用各种三氟甲磺酸酯和二芳基-，二烷基-和烷基芳基膦-硼烷前体证明了该方法的多功能性。手性对映体纯的膦硼烷是从手性三氟甲磺酸酯合成的。