(3S,6R,9R,12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl-3,6,9,12-tetraphosphatetradecane | 879329-27-8

• 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: (3S,6R,9R,12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl-3,6,9,12-tetraphosphatetradecane
• 英文别名: (S)-tert-butyl-[2-[tert-butyl-[2-[tert-butyl-[2-[tert-butyl(methyl)phosphanyl]ethyl]phosphanyl]ethyl]phosphanyl]ethyl]-methylphosphane
• CAS: 879329-27-8
• 化学式: C₂₄H₅₄P₄
• 分子量: 466.588
• InChiKey: ZDPSNVXYFAPFRD-YVHASNINSA-N

物化性质

• 沸点：
  502.4±45.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  28
• 可旋转键数：
  13
• 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：
  0

反应信息

• 作为反应物：
  描述：

  chloro(1,5-cyclooctadiene)(pentamethylcyclopentadiene)ruthenium(II) 、 (3S,6R,9R,12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl-3,6,9,12-tetraphosphatetradecane 以 二氯甲烷 为溶剂， 以35%的产率得到[(RuCl(η5-C5Me5))2((3S,6R,9R,12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl-3,6,9,12-tetraphosphatetradecane)]
  参考文献：
  名称：

  Construction of optically active multimetallic systems of rhodium(I), palladium(II), and ruthenium(II) with a P-chiral tetraphosphine ligand

  摘要：

  The treatment of optically P-chiral tetraphosphine, (3S, 6R, 9R, 12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl3,6,9,12-tetraphosphatetradecane (1), with rhodium(I), palladium(II), and ruthenium( II) complex precursors led to the selective formation of mono-, di-, or trinuclear homo- or heterometallic complexes, [Rh(1)]SbF6 (4), [{Rh(nbd)}(2)(1)](SbF6)(2) (3), [{Pd(eta(3)-allyl)} 2(1)](SbF6)(2) (5), [{RuCl(eta(5)-C-5(CH3)(5))}(2)(1)] (6), and [{RuCl2(eta(6)-benzene)}(2)(PdCl2)(1)] (8). These complexes were characterized by NMR and X-ray crystallographic analysis. (C) 2008 Elsevier B. V. All rights reserved.

  DOI：

  10.1016/j.jorganchem.2008.10.014

文献信息

• <i>P</i>-Chiral Tetraphosphine Dirhodium Complex as a Catalyst for Asymmetric Hydrogenation:  Synthesis, Structure, Enantioselectivity, and Mechanism. Stereoselective Formation of a Dirhodium Tetrahydride Complex and Its Reaction with Methyl (<i>Z</i>)-α-Acetamidocinnamate
  作者：Tsuneo Imamoto、Keiji Yashio、Karen V. L. Crépy、Kosuke Katagiri、Hidetoshi Takahashi、Mitsuhiro Kouchi、Ilya D. Gridnev

  DOI：10.1021/om050759p

  日期：2006.2.1

  probed as a catalyst in asymmetric hydrogenations of representative prochiral substrates, demonstrating high activity and good to excellent enantioselectivities. A mechanistic study revealed that 5 can be cleanly and stereoselectively converted to the tetrahydride species 6a, which is stable up to 0 °C and at higher temperatures slowly decomposes without the loss of hydrogen. The low-temperature (−80 °C)

  通过膦-硼烷方法制备旋光的C 2-对称的四膦4。其dirhodium配合物5在结构上得到了表征，并被用作代表性前手性底物的不对称氢化中的催化剂，证明了其高活性和良好至出色的对映选择性。机理研究表明，可以干净地和立体选择性地将5转化为四氢化物物种6a，该物种在0°C时稳定，并且在较高的温度下缓慢分解而不会损失氢。低温（-80℃）的反应图6a与甲基（ž）-α-乙酰氨基doc酸酯（MAC）干净地得到四氢化物配合物7，该四氢化物配合物7包含仅通过酰胺羰基配位的一分子底物分子，而底物的双键保持不配位。将温度升高到-40°C导致络合物7到8发生不可逆的异构化，这与7的区别仅在于配体的空间排列。与7至8的异构化同时进行的迁移插入产生三氢化物络合物9，其是前述的一氢化物中间体的类似物。当6a反应用MAC在过量MAC的存在下进行分离，释放的铑配合物被底物捕获，得到催化剂-底物配合物10，用多核NMR表征。与
• Construction of optically active multimetallic systems of rhodium(I), palladium(II), and ruthenium(II) with a P-chiral tetraphosphine ligand
  作者：Keiji Yashio、Masatoshi Kawahata、Hiroshi Danjo、Kentaro Yamaguchi、Masaharu Nakamura、Tsuneo Imamoto

  DOI：10.1016/j.jorganchem.2008.10.014

  日期：2009.1

  The treatment of optically P-chiral tetraphosphine, (3S, 6R, 9R, 12S)-6,9-di-tert-butyl-2,2,3,12,13,13-hexamethyl3,6,9,12-tetraphosphatetradecane (1), with rhodium(I), palladium(II), and ruthenium( II) complex precursors led to the selective formation of mono-, di-, or trinuclear homo- or heterometallic complexes, [Rh(1)]SbF6 (4), [Rh(nbd)}(2)(1)](SbF6)(2) (3), [Pd(eta(3)-allyl)} 2(1)](SbF6)(2) (5), [RuCl(eta(5)-C-5(CH3)(5))}(2)(1)] (6), and [RuCl2(eta(6)-benzene)}(2)(PdCl2)(1)] (8). These complexes were characterized by NMR and X-ray crystallographic analysis. (C) 2008 Elsevier B. V. All rights reserved.