(R,R)-bis((boranato(tert-butyl)methyl)phosphino)methane | 224618-25-1

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: (R,R)-bis((boranato(tert-butyl)methyl)phosphino)methane
• 英文别名: t-Bu-MiniPHOS*2BH3；(R,R)-bis(t-butylmethylphosphino)methane diborane；[(Boranuidyl-tert-butyl-methylphosphaniumyl)methyl-tert-butyl-methylphosphaniumyl]boranuide；[(boranuidyl-tert-butyl-methylphosphaniumyl)methyl-tert-butyl-methylphosphaniumyl]boranuide
• CAS: 224618-25-1；265298-62-2；1326304-73-7
• 化学式: C₁₁H₃₂B₂P₂
• 分子量: 247.945
• InChiKey: FVRCRDVUHYQRPX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R,R)-bis((boranato(tert-butyl)methyl)phosphino)methane 在 三乙烯二胺 、 sulfur 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 (R,R)-bis[(t-butyl)methylphosphinothioyl]methane
  参考文献：
  名称：

  One-ligand Catalytic Asymmetric Deprotonation of a Phosphine Borane: Synthesis of P-Stereogenic Bisphosphine Ligands

  摘要：

  A new protocol for the catalytic asymmetric deprotonation of a phosphine borane using s-BuLi and sub-stoichiometric quantities of chiral diamines is reported. The method involves three sequential additions of s-BuLi, and use of (-)-sparteine or the (+)-sparteine surrogate facilitates access to P-stereogenic phosphines with opposite configuration. The method is exemplified by the catalytic asymmetric synthesis of each enantiomer of precursors to QuinoxP*, trichickenfootphos, and Mini-PHOS.

  DOI：

  10.1021/jo200708e
• 作为产物：
  描述：

  (S)-tert-butylmethylphosphine-borane 在 正丁基锂 、 sodium hydride 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 1.25h， 生成 (R,R)-bis((boranato(tert-butyl)methyl)phosphino)methane
  参考文献：
  名称：

  旋光性二级膦-硼烷的利用：铑催化的不对称氢化中P-手性二膦的合成及其对映体诱导能力

  摘要：

  叔丁基甲基膦-硼烷的两种对映体均已用于合成手性二膦和/或其硼烷配合物。1,2-双（叔丁基甲基膦基）乙烷的对映体硼烷络合物（t -Bu-BisP ∗）是由仲膦-硼烷和1,2-二氯乙烷高收率制备的。制备了t -Bu-MiniPHOS的单螯合Rh络合物，并在某些代表性官能化烯烃的不对称加氢中检测了其催化活性。还描述了具有喹啉或喹喔啉骨架的三个新的P-手性膦配体的合成及其对映体诱导能力。

  DOI：

  10.1016/j.tet.2015.05.088

文献信息

• Optically Active Dinuclear Palladium Complexes Containing a Pd−Pd Bond: Preparation and Enantioinduction Ability in Asymmetric Ring-Opening Reactions
  作者：Tomokazu Ogura、Kazuhiro Yoshida、Akira Yanagisawa、Tsuneo Imamoto

  DOI：10.1021/ol900533h

  日期：2009.6.4

  Optically active dinuclear palladium complexes containing a Pd−Pd bond were prepared by using (R,R)-bis(tert-butylmethylphosphino)methane ((R,R)-t-Bu-MiniPHOS). The dinuclear palladium complexes coupled with silver triflate exhibited good to excellent enantioselectivities up to 99% in palladium-catalyzed alkylative ring-opening reactions of azabenzonorbornadienes.

  通过使用（R，R）-双（叔丁基甲基膦基）甲烷（（R，R）-t -Bu-MiniPHOS）制备包含Pd-Pd键的旋光性双核钯配合物。在三氮杂苯并降冰片二烯的钯催化的烷基化开环反应中，双核钯配合物与三氟甲磺酸银偶联显示良好至优异的对映选择性，高达99％。
• Improved synthetic routes to methylene-bridged P-chiral diphosphine ligands via secondary phosphine–boranes
  作者：Tsuneo Imamoto、Ken Tamura、Tomokazu Ogura、Yui Ikematsu、Daisuke Mayama、Masashi Sugiya

  DOI：10.1016/j.tetasy.2010.03.025

  日期：2010.6

  Improved methods for the preparation of methylene-bridged diphosphine ligands are described. Both enantiomers of the key intermediate tert-butylmethylphosphine–borane were prepared via resolution or by the conversion of one enantiomer into the opposite enantiomer. The precursor borane complexes of bis(tert-butylmethylphosphino)methane (t-Bu-MiniPHOS), bis((1,1,3,3-tetramethylbutyl)methylphosphino)methane

  描述了制备亚甲基桥接的二膦配体的改进方法。关键中间体叔丁基甲基膦-硼烷的两种对映体都是通过拆分或将一种对映体转化为相反的对映体而制得的。之二的前体硼烷配合物（叔-butylmethylphosphino）甲烷（吨-Bu-MiniPHOS），双（（1,1,3,3-四甲基丁基）甲基膦）甲烷（吨-辛MiniPHOS）和（叔-butylmethylphosphino） （二叔丁基膦基）甲烷（trichickenfootphos）以高收率和对映纯形式制备。
• Utilization of optically active secondary phosphine–boranes: synthesis of P-chiral diphosphines and their enantioinduction ability in rhodium-catalyzed asymmetric hydrogenation
  作者：Tsuneo Imamoto、Yumi Horiuchi、Eri Hamanishi、Satoshi Takeshita、Ken Tamura、Masashi Sugiya、Kazuhiro Yoshida

  DOI：10.1016/j.tet.2015.05.088

  日期：2015.9

  have been used for the synthesis of P-chiral diphosphines and/or their borane complexes. The enantiopure borane complex of 1,2-bis(tert-butylmethylphosphino)ethane (t-Bu-BisP∗) was prepared in high yield from the secondary phosphine–borane and 1,2-dichloroethane. A mono-chelated Rh-complex of t-Bu-MiniPHOS was prepared and its catalytic activity was examined in the asymmetric hydrogenation of some representative

  叔丁基甲基膦-硼烷的两种对映体均已用于合成手性二膦和/或其硼烷配合物。1,2-双（叔丁基甲基膦基）乙烷的对映体硼烷络合物（t -Bu-BisP ∗）是由仲膦-硼烷和1,2-二氯乙烷高收率制备的。制备了t -Bu-MiniPHOS的单螯合Rh络合物，并在某些代表性官能化烯烃的不对称加氢中检测了其催化活性。还描述了具有喹啉或喹喔啉骨架的三个新的P-手性膦配体的合成及其对映体诱导能力。
• One-ligand Catalytic Asymmetric Deprotonation of a Phosphine Borane: Synthesis of <i>P</i>-Stereogenic Bisphosphine Ligands
  作者：Johan Granander、Francesco Secci、Steven J. Canipa、Peter O’Brien、Brian Kelly

  DOI：10.1021/jo200708e

  日期：2011.6.3

  A new protocol for the catalytic asymmetric deprotonation of a phosphine borane using s-BuLi and sub-stoichiometric quantities of chiral diamines is reported. The method involves three sequential additions of s-BuLi, and use of (-)-sparteine or the (+)-sparteine surrogate facilitates access to P-stereogenic phosphines with opposite configuration. The method is exemplified by the catalytic asymmetric synthesis of each enantiomer of precursors to QuinoxP*, trichickenfootphos, and Mini-PHOS.