| 477338-17-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• CAS: 477338-17-3
• 化学式: C₃₇H₄₄O₃P₂
• 分子量: 598.702
• InChiKey: FYTQDKXPKIUNRC-RWYGWLOXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  11.02
• 重原子数：
  42.0
• 可旋转键数：
  4.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  35.51
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  [bis(2-methylallyl)cycloocta-1,5-diene]ruthenium(II) 、 以 正己烷 为溶剂， 以28%的产率得到
  参考文献：
  名称：

  Synthesis, Characterization, and Reactivity of Ruthenium Bis-Allyl Complexes with Chiral Phosphine-Phosphite Ligands

  摘要：

  A series of ruthenium bis-allyl complexes of formula Ru(eta(3)-2-MeC3H4)(2)(P-OP) (I) which incorporate chiral phosphine-phosphite ligands (P-OP) have been prepared and characterized. Compounds I exist in solution as a mixture of two diastereomers (maj and min) differing in the configuration at the metal. Both isomers are in equilibrium in solution, and their ratio varies with the nature of the P-OP ligand. Along the series, higher values of the maj/min ratio were observed with complexes bearing less sterically encumbered phosphite groups. In reactions of compounds I with protic reagents removal of one or two ally! ligands has been observed. Thus, reaction of 1h with pentachlorophenol produces the mixed allyl-phenoxide 3h, whereas reaction of la or 1h with tiglic acid produces the corresponding tiglates 4a,h, respectively. In addition, compounds I generate active catalysts for the hydrogenation of tiglic and 2-methyl-2-pentenoic acids. By appropriate optimization of the structure of the P-OP ligand, enantioselectivities up to 89% ee were obtained in these reactions. In addition, complexes I also catalyze the ROMP reaction of norbornene, although low initiation rates have been observed for this process.

  DOI：

  10.1021/om300018s

文献信息

• Electronic Differences between Coordinating Functionalities of Chiral Phosphine−Phosphites and Effects in Catalytic Enantioselective Hydrogenation
  作者：Andrés Suárez、Miguel A. Méndez-Rojas、Antonio Pizzano

  DOI：10.1021/om020140c

  日期：2002.10.1

  electron density at the metal center compared with diphosphine analogues. The distinct nature of the phosphorus functionalities has also been evidenced in rhodium-catalyzed enantioselective hydrogenation of methyl Z-α-acetamido-cinnamate (MAC). Thus, the coordination mode of the substrate is governed by the chiral ligand, directing the olefinic bond to a cis position with respect to the phosphite group,

  已经描述了新型手性膦-亚磷酸酯（P-OP）的便捷合成。所开发的合成方案的多功能性允许制备具有不同膦片段的配体，并选择了立体定位元件的位置。1 J PSe的值分析相应的二硒化物的膦酸酯与亚磷酸酯片段相对于膦基的预期的较低的σ供体能力以及在甲基取代苯基取代基之后的膦碱度增加是一致的。检查一系列配合物RhCl（CO）（P-OP）上的υ（CO）值表明亚磷酸酯基团具有可变的π受体能力，补偿了膦官能团碱性的变化，并且具有相当大的与二膦类似物相比，降低了金属中心的电子密度。磷官能团的独特性质也已在铑催化的甲基Z的对映选择性加氢中得到证明-α-乙酰氨基肉桂酸酯（MAC）。因此，如[Rh（P-OP）（MAC）] +配合物进行的NMR研究表明，底物的配位模式由手性配体控制，将烯键指向相对于亚磷酸酯基团的顺式位置。。结果，亚磷酸酯基团对产物的对映选择性具有更大的影响。然而，该方法的光学纯度还取决于膦基的性质，因