(S_P,S_P)-(-)-(E)-ethene-1,2-diylbis[methyl(phenyl)phosphine] dioxide | 124151-53-7

• 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: (S_P,S_P)-(-)-(E)-ethene-1,2-diylbis[methyl(phenyl)phosphine] dioxide
• 英文别名: [methyl-[(E)-2-[methyl(phenyl)phosphoryl]ethenyl]phosphoryl]benzene
• CAS: 124151-53-7
• 化学式: C₁₆H₁₈O₂P₂
• 分子量: 304.265
• InChiKey: FTZLCYCZHAIWKB-JAPHFTBRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.12
• 拓扑面积：
  34.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (-)-(S)-methylphenylvinylphosphine oxide 在 吡啶 、 氯 、 三乙胺 作用下， 反应 24.0h， 生成 (S_P,S_P)-(-)-(E)-ethene-1,2-diylbis[methyl(phenyl)phosphine] dioxide
  参考文献：
  名称：

  旋光氧化膦。8 1：非对称1,2-二膦基乙烯的合成及相关体系

  摘要：

  非对称和旋光反式的合成已经完成了-1，2-二膦基乙烯。所采用的加成-消除途径可能是通用的，并且利用了容易获得的仲膦氧化物和叔1-卤代戊基膦氧化物氧化物。立体拥挤的仲氧化膦通过与相应的1-溴乙烯基氧化膦在吡啶中加热直接直接提供不对称的1,2-二膦亚基乙烯。对于其他仲膦氧化物，涉及相应的1-氯乙烯基膦氧化物的两步法是更有利的。在导致光学活性1的合成中 具有等价或非等价手性磷中心的2-二膦基乙烯中心已利用新型的同型手性（-）-（1-溴乙烯基）甲基苯基膦氧化物和（-）-（1-氯乙烯基）甲基苯基膦氧化物提供了非常实用的自拆分系统一个手性磷中心分解另一个。所开发的方法也已用于合成含有一个磷和一个硫活化基团的类似的双活化乙烯。

  DOI：

  10.1016/0040-4020(89)80061-4

文献信息

• Optically active phosphine oxides. 8
  作者：K. Milchał Pietrusiewicz、Witold Wisniewski、Maria Zabłocka

  DOI：10.1016/0040-4020(89)80061-4

  日期：1989.1

  1-bromovinyl phosphine oxide in pyridine. For other secondary phosphine oxides a two-step procedure involving corresponding 1-chlorovinyl phosphine oxides is more advantageous. In the syntheses leading to the optically active 1,2-diphosphinylethenes possessing either equivalent or nonequivalent chiral phosphorus centres the novel homochiral (-)-(1-bromovinyl) methylphenylphosphine oxide and (-)-(1-chlorovinyl)

  非对称和旋光反式的合成已经完成了-1，2-二膦基乙烯。所采用的加成-消除途径可能是通用的，并且利用了容易获得的仲膦氧化物和叔1-卤代戊基膦氧化物氧化物。立体拥挤的仲氧化膦通过与相应的1-溴乙烯基氧化膦在吡啶中加热直接直接提供不对称的1,2-二膦亚基乙烯。对于其他仲膦氧化物，涉及相应的1-氯乙烯基膦氧化物的两步法是更有利的。在导致光学活性1的合成中 具有等价或非等价手性磷中心的2-二膦基乙烯中心已利用新型的同型手性（-）-（1-溴乙烯基）甲基苯基膦氧化物和（-）-（1-氯乙烯基）甲基苯基膦氧化物提供了非常实用的自拆分系统一个手性磷中心分解另一个。所开发的方法也已用于合成含有一个磷和一个硫活化基团的类似的双活化乙烯。
• Nitro-Substituted Hoveyda−Grubbs Ruthenium Carbenes:  Enhancement of Catalyst Activity through Electronic Activation
  作者：Anna Michrowska、Robert Bujok、Syuzanna Harutyunyan、Volodymyr Sashuk、Grigory Dolgonos、Karol Grela

  DOI：10.1021/ja048794v

  日期：2004.8.1

  The design, synthesis, stability, and catalytic activity of nitro-substituted Hoveyda-Grubbs metathesis catalysts are described. The highly active and stable meta- and para-substituted complexes are attractive from a practical point of view. These catalysts operate in very mild conditions and can be successfully applied in various types of metathesis [ring-closing metathesis, cross-metathesis (CM), and enyne metathesis]. Although the presence of a NO2 group leads to catalysts that are dramatically more active than both the second-generation Grubbs's catalyst and the phosphine-free Hoveyda's carbene, enhancement of reactivity is somewhat lower than that observed for a sterically activated Hoveyda-Grubbs catalyst. Attempts to combine two modes of activation, steric and electronic, result in severely decreasing a catalyst's stability. The present findings illustrate that different Ru catalysts turned out to be optimal for different applications. Whereas phosphine-free carbenes are catalysts of choice for CM of various electron-deficient substrates, they exhibit lower reactivity in the formation of tetrasubstituted double bonds. This demonstrates that no single catalyst outperforms all others in all possible applications.
• Synthesis of Substituted <i>P</i>-Stereogenic Vinylphosphine Oxides by Olefin Cross-Metathesis
  作者：Oleg M. Demchuk、K. Michał Pietrusiewicz、Anna Michrowska、Karol Grela

  DOI：10.1021/ol035011m

  日期：2003.9.1

  [GRAPHICS]Substituted vinylphosphine oxides have been prepared in good yield and exclusive (E)-olefin selectivity via olefin cross-metathesis using Grubbs and Hoveyda-type ruthenium catalysts. In addition, metathesis of chiral vinylphosphine oxides proceeds without racemization of the phosphorus chirality center, providing easy access to functionalized chiral nonracemic (E)-alkenylphosphine oxides.
• PIETRUSIEWICZ, K. MICHAL;WISNIEWSKI, WITOLD;ZABLOCKA, MARIA, TETRAHEDRON, 45,(1989) N, C. 337-348
  作者：PIETRUSIEWICZ, K. MICHAL、WISNIEWSKI, WITOLD、ZABLOCKA, MARIA

  DOI：——

  日期：——
• Homo- and Cross-Olefin Metathesis Coupling of Vinylphosphane Oxides and Electron-Poor Alkenes: Access to P-Stereogenic Dienophiles
  作者：Nikolai Vinokurov、Anna Michrowska、Anna Szmigielska、Zbigniew Drzazga、Grzegorz Wójciuk、Oleg M. Demchuk、Karol Grela、K. Michał Pietrusiewicz、Holger Butenschön

  DOI：10.1002/adsc.200505463

  日期：2006.5

  Vinylphosphane oxides 6 undergo catalytic olefin homo-metathesis leading to achiral and P-stereogenic diphosphane dioxides 7 with exclusive (E)-selectivity. Similarly, EWG-substituted vinylphosphane oxides 11, 12 could be prepared with complete (E)-olefin selectivity via olefin cross-metathesis with electron-deficient substrates, such as methyl acrylate and 2-fluorostyrene, using nitro-Hoveyda ruthenium

  乙烯基膦氧化物6经历催化的烯烃均复分解，从而产生具有排他的（E）-选择性的非手性和P-立体异构的二膦二氧化物7。类似地，EWG取代vinylphosphane氧化物11，12可以与完整的（制备ë）烯烃选择性通过烯烃交叉复分解反应用缺电子的底物，如丙烯酸甲酯和2-氟苯乙烯，使用硝基加入Hoveyda钌预催化剂III。手性非外消旋乙烯基膦氧化物的交叉复分解和均复分解没有手性的磷中心外消旋化。