tert-butyl(dimethyl)phosphine borane

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: tert-butyl(dimethyl)phosphine borane
• 英文别名: borane;tert-butyl(dimethyl)phosphane
• 化学式: BH₃*C₆H₁₅P
• 分子量: 131.994
• InChiKey: MHAGKNYBOOCWIH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.34
• 重原子数：
  8.0
• 可旋转键数：
  0.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  tert-butyl(dimethyl)phosphine borane 在 仲丁基锂 、 氧气 作用下， 以 乙醚 、 环己烷 为溶剂， 反应 20.0h， 以57%的产率得到(R)-叔丁基(羟甲基)甲基膦硼烷
  参考文献：
  名称：

  Catalytic Asymmetric Synthesis of Ferrocenes and P-Stereogenic Bisphosphines

  摘要：

  The catalytic asymmetric synthesis of planar chiral ferrocenes and P-stereogenic phosphines and bisphosphines (important classes of chiral ligands for metal-catalyzed asymmetric processes) is successfully demonstrated using n-BuLi or s-BuLi in combination with substoichiometric quantities (0.1-0.5 equiv) of (-)-sparteine or the (+)-sparteine surrogate.

  DOI：

  10.1021/ja062616f
• 作为产物：
  描述：

  甲基氯化镁 、 alkaline earth salt of/the/ methylsulfuric acid 在 三氯化磷 、 硼烷四氢呋喃络合物 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以94%的产率得到tert-butyl(dimethyl)phosphine borane
  参考文献：
  名称：

  Asymmetric Hydrogenation Catalyzed by (S,S)-R-BisP*-Rh and (R,R)-R-MiniPHOS Complexes: Scope, Limitations, and Mechanism

  摘要：

  A new class of chiral C-2-symmetric bis(trialkyl)phosphine ligands has been prepared and used in Rh(I)-catalyzed asymmetric hydrogenation reactions. The Ligands, 1,2-bis(alkylmethylphosphino)ethanes 1 a-g (abbreviated as BisP*, alkyl = t-butyl, 1-adamantyl, 1-methylcyclohexyl, 1,1-diethylpropyl, cyclopentyl, cyclohexyl, isopropyl) and 1,2-bis(alkylmethylphosphino)methanes 2 a-d (abbreviated as MiniPHOS, alkyl = t-butyl, cyclohexyl, isopropyl, phenyl) are prepared by a simple synthetic approach based on the air-stable phosphine-boranes. These new ligands give the corresponding Rh(I) complexes, which are effective catalytic precursors for the asymmetric hydrogenation of a representative series of dehydroamino acids and itaconic acid derivatives. Enantioselectivities observed in these hydrogenations are universally high and in many cases exceed 99%. X-Ray characterization of four precatalysts, study of the pressure effects, deuteration experiments, and characterization of the wide series of intermediates in the catalytic cycle are used for the discussion of the possible correlation between the structure of the catalysts and the outcome of the catalytic asymmetric hydrogenation.

  DOI：

  10.1002/1615-4169(20010129)343:1<118::aid-adsc118>3.3.co;2-q

文献信息

• Desymmetrization of Prochiral Phosphanes Using Derivatives of (−)-Cytisine
  作者：Magnus J. Johansson、Lennart O. Schwartz、Mohamed Amedjkouh、Nina C. Kann

  DOI：10.1002/ejoc.200400006

  日期：2004.5

  yHistorically, (-)-sparteine-sec-BuLi has been used to desym-metrize prochiral phosphanes. In this report, derivatives of an alkaloid extracted from the seeds of Laburnum anagyro-ides have been utilized to mimic (+)-sparteine, which is not readily available. In several cases, the enantioselectivities achieved with the (+)-Sparteine surrogates outperformed (-)-sparteine itself in the deprotonation of

  y历史上，(-)-sparteine-sec-BuLi 已被用于去对称化前手性膦。在这份报告中，从 Laburnum anagyro-ides 种子中提取的生物碱衍生物已被用来模拟 (+)-sparteine，这是不容易获得的。在一些情况下，在烷基取代（以及芳基取代）前手性膦衍生物的去质子化过程中，使用 (+)-Sparteine 替代物实现的对映选择性优于 (-)-sparteine 本身。此外，这些替代物的使用为磷化学中的手性转换提供了一种新方法。((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)。
• Intramolecular Staudinger Ligation towards Biaryl-Containing Lactams
  作者：Jan van Maarseveen、Géraldine Masson、Tim Hartog、Hans Schoemaker、Henk Hiemstra

  DOI：10.1055/s-2006-939059

  日期：——

  Both 15- and 16-membered biaryl-type lactams were prepared in good yield using the intramolecular Staudinger ligation strategy.

  利用分子内施陶丁格连接策略，制备了 15 元和 16 元双芳族内酰胺，收率良好。
• Modular Asymmetric Synthesis of P-Chirogenic β-Amino Phosphine Boranes
  作者：Magnus J. Johansson、Kristian H. O. Andersson、Nina Kann

  DOI：10.1021/jo800672b

  日期：2008.6.1

  A short concise route to beta-aminophosphine boranes is presented via the desymmetrization of prochiral phosphine boranes, forming P-chirogenic aldehydes that are rapidly transformed to the target compounds employing reductive amination under microwave irradiation. This sequence provides a modular route to P-chirogenic P,N ligands, and in addition, the intermediate aldehydes are versatile P-chiral building blocks for ligand design in general. An alternative pathway via the corresponding alpha-carboxyphosphines is also described. The ligands were subsequently evalutated in the asymmetric conjugate addition of diethylzinc to trans-/beta-nitrostyrene.
• Asymmetric Hydrogenation Catalyzed by (S,S)-R-BisP*-Rh and (R,R)-R-MiniPHOS Complexes: Scope, Limitations, and Mechanism
  作者：Ilya D. Gridnev、Yoshinori Yamanoi、Natsuka Higashi、Hideyuki Tsuruta、Masaya Yasutake、Tsuneo Imamoto

  DOI：10.1002/1615-4169(20010129)343:1<118::aid-adsc118>3.3.co;2-q

  日期：2001.1.29

  A new class of chiral C-2-symmetric bis(trialkyl)phosphine ligands has been prepared and used in Rh(I)-catalyzed asymmetric hydrogenation reactions. The Ligands, 1,2-bis(alkylmethylphosphino)ethanes 1 a-g (abbreviated as BisP*, alkyl = t-butyl, 1-adamantyl, 1-methylcyclohexyl, 1,1-diethylpropyl, cyclopentyl, cyclohexyl, isopropyl) and 1,2-bis(alkylmethylphosphino)methanes 2 a-d (abbreviated as MiniPHOS, alkyl = t-butyl, cyclohexyl, isopropyl, phenyl) are prepared by a simple synthetic approach based on the air-stable phosphine-boranes. These new ligands give the corresponding Rh(I) complexes, which are effective catalytic precursors for the asymmetric hydrogenation of a representative series of dehydroamino acids and itaconic acid derivatives. Enantioselectivities observed in these hydrogenations are universally high and in many cases exceed 99%. X-Ray characterization of four precatalysts, study of the pressure effects, deuteration experiments, and characterization of the wide series of intermediates in the catalytic cycle are used for the discussion of the possible correlation between the structure of the catalysts and the outcome of the catalytic asymmetric hydrogenation.
• Catalytic Asymmetric Synthesis of Ferrocenes and <i>P</i>-Stereogenic Bisphosphines
  作者：Cédric Genet、Steven J. Canipa、Peter O'Brien、Sven Taylor

  DOI：10.1021/ja062616f

  日期：2006.7.1

  The catalytic asymmetric synthesis of planar chiral ferrocenes and P-stereogenic phosphines and bisphosphines (important classes of chiral ligands for metal-catalyzed asymmetric processes) is successfully demonstrated using n-BuLi or s-BuLi in combination with substoichiometric quantities (0.1-0.5 equiv) of (-)-sparteine or the (+)-sparteine surrogate.