rac-tert-butylmethylphosphineborane(methyl)dimethylphenylsilane | 1203661-04-4

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: rac-tert-butylmethylphosphineborane(methyl)dimethylphenylsilane
• CAS: 1203661-04-4
• 化学式: C₁₄H₂₈BPSi
• 分子量: 266.247
• InChiKey: FQTSTNGYGWGNMD-MRXNPFEDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.87
• 重原子数：
  17.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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：

  苯基二甲基氯硅烷 、 叔丁基二甲基膦硼烷 在 仲丁基锂 、 鹰爪豆碱 作用下， 以 乙醚 为溶剂， 以76%的产率得到rac-tert-butylmethylphosphineborane(methyl)dimethylphenylsilane
  参考文献：
  名称：

  膦硼烷和硫化物的催化不对称去质子化反应是生成P-立体异构化合物的途径。

  摘要：

  使用有机锂和亚化学计量量的（-）-天冬氨酸在膦硼烷和硫化物催化不对称脱质子化反应中的比较显示出在硫化膦脱质子化中的优异催化效率。

  DOI：

  10.1039/b806864j

文献信息

• Catalytic asymmetric deprotonation of a phosphine borane: comparison of two-ligand and one-ligand catalysis
  作者：Steven J. Canipa、Peter O’Brien、Sven Taylor

  DOI：10.1016/j.tetasy.2009.10.002

  日期：2009.10

  The catalytic asymmetric deprotonation of tert-butyldimethylphosphine borane using s-BuLi or n-BuLi and sub-stoichiometric amounts of (−)-sparteine under one-ligand and two-ligand manifolds has been investigated. Using s-BuLi, slightly higher enantioselectivity was obtained using two-ligand catalysis (use of sub-stoichiometric (−)-sparteine in the presence of a stoichiometric amount of a second achiral

  研究了在s- BuLi或n -BuLi的催化下，叔丁基二甲基膦硼烷的催化不对称脱质子反应，以及在一配体和二配体歧管下亚化学计量的（-）-天冬氨酸。与单配体催化（使用亚配体催化）相比，使用s- BuLi时，使用双配体催化（在化学计量的第二个非手性配体存在下使用亚化学计量的（-）-天冬氨酸）可获得更高的对映选择性。化学计量的（-）-半胱氨酸）。用n使用LiDMAE（DMAE =二甲基氨基乙醇）作为化学计量配体的BuBu两配体催化是获得良好收率和对映选择性的唯一方法。在这种情况下，由于（-）-天冬氨酸未被翻转，单配体催化失败。
• [RuCl₂(η⁶-<i>p</i>-cymene)(P*)] and [RuCl₂(κ-P*-η⁶-arene)] Complexes Containing<i>P</i>-Stereogenic Phosphines. Activity in Transfer Hydrogenation and Interactions with DNA
  作者：Rosario Aznar、Arnald Grabulosa、Alberto Mannu、Guillermo Muller、Daniel Sainz、Virtudes Moreno、Mercè Font-Bardia、Teresa Calvet、Julia Lorenzo

  DOI：10.1021/om3012294

  日期：2013.4.22

  [RuCl2(κ-P*-η6-arene)] compounds. Full characterization of all compounds both in solution and in the solid state has been carried out. Crystal structure determinations of four phosphine–borane molecules confirm the S configuration at the phosphorus atom (1a,e,l and 2d). Moreover, the crystal structure of one p-cymene complex (5i) and four tethered complexes reveal the strain of the compounds with two atoms

  一系列半夹心钌络合物，将[RuCl的的制备2（η 6 - p（P * =（P *）-cymene）]小号-PMeRR'）和将[RuCl 2（κ-P *-η 6 - （芳烃）]，据报道含有P-立体生成的膦。通过添加（H 3 B）PMe 2 R（R = t -Bu （1），Cy（2），Fc（3））/秒获得硼烷保护的P-立体异构膦。-BuLi /（-）-天冬氨酸加成至苄基卤化物，羰基官能团和环氧化物的收率在40％至90％之间，ee值在70-99％范围内。那些含有芳基次要功能已在将[RuCl的制备中被使用2（η 6 - p复合物（P *）-cymene）]。除（H 3 B）PRMe（CH 2 SiMe 2 Ph）膦外，硼烷已使用HBF 4进行了脱保护，其中DABCO用于避免CH 2 -Si键的部分断裂。在（H 3 B）P（t -Bu）Me（CH 2 C（OH）Ph 2）（1l）获得脱水的膦。除了在
• P-Stereogenic monophosphines in Pd-catalysed enantioselective hydrovinylation of styrene
  作者：Arnald Grabulosa、Alberto Mannu、Guillermo Muller、Teresa Calvet、Mercè Font-Bardia

  DOI：10.1016/j.jorganchem.2011.02.034

  日期：2011.6

  Two groups of P-stereogenic monodentate phosphines containing pendant groups bearing functionalities capable of having secondary interactions, PArPhR (Ar = 2-[(2',6'-dimethoxy)-1,1'-biphenylyl] and R = OMe (6) or Me (8)) and PMeR(CH2R') (13, R t-Bu or 14 R Fc and R' SiMe3 (a), SiMe2Ph (b) or CH2(2-naphthyl) (c)) have been prepared in enantiomerically pure form by the Juge and Evans methodologies and characterised, including the crystal structure for the borane adduct of 12b. Reaction of the phosphines with the Pd dimer [Pd(eta(3)-2-Me-allyl)(mu-Cl)](2) produced neutral allylic complexes C [PdCl (eta(3)-2-Me-C3H4)P*], which have been characterised in solution and shown to be a mixture of isomers with different absolute configuration at the Pd atom. After abstraction of the chloride ligand by AgBF4, the solutions of cationic complexes have been used as catalyst precursors in the hydrovinylation of styrene under mild conditions. Very good activities (up to 1015 h(-1)), moderate to good selectivities to 3-phenyl-1-butene and low to moderate enantioselectivities (< 45% ee) have been found. Deep differences in the activity and enantioselectivity have been found depending on the structure of the ligand. In spite of that the results did not permit to confirm the improvement of the selectivities of the reaction by stabilization of the catalyst through secondary coordination with the potentially hemilabile ligands. (C) 2011 Elsevier B.V. All rights reserved.