[2-(4,8-Ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-dimethylphosphane | 412050-21-6

• 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: [2-(4,8-Ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-dimethylphosphane
• CAS: 412050-21-6
• 化学式: C₃₂H₄₂O₃P₂
• 分子量: 536.631
• InChiKey: VJRFZMWRASFUJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  37
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 [2-(4,8-Ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-dimethylphosphane 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  手性膦-亚磷酸酯的配位功能与催化对映选择性加氢作用之间的电子差异

  摘要：

  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

  DOI：

  10.1021/om020140c
• 作为产物：
  描述：

  (CH3)2P(C6H4OCH3-2) 在 三溴化硼 、 三乙胺 作用下， 生成 [2-(4,8-Ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-dimethylphosphane
  参考文献：
  名称：

  New chiral phosphine–phosphites: a convenient synthesis based on the demethylation of o-anisyl phosphines and application in highly enantioselective catalytic hydrogenations

  摘要：

  An easy demethylation of o-anisyl phosphines provides a convenient access to a series of new chiral phosphine-phosphites. The screening of these derivatives as ligands in rhodium-catalyzed asymmetric hydrogenation of dimethyl itaconate has shown a profound influence of ligand structure on the enantioselectivity of the process. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(01)00464-5

文献信息

• Asymmetric Hydroformylation of Olefins with Rh Catalysts Modified with Chiral Phosphine−Phosphite Ligands
  作者：Miguel Rubio、Andrés Suárez、Eleuterio Álvarez、Claudio Bianchini、Werner Oberhauser、Maurizio Peruzzini、Antonio Pizzano

  DOI：10.1021/om700744b

  日期：2007.12.1

  designed chiral phosphine−phosphite ligands (P−OP) have been tested in the asymmetric hydroformylation of styrene, vinyl naphthalenes, and allyl cyanide. Based on single-crystal X-ray diffraction analysis and NMR studies, restricted aryl rotation has been found to characterize ligands 1e and 1f. The outcome of the rhodium-catalyzed hydroformylation reactions is highly dependent on the nature of the two

  通过模块化设计的手性膦-亚磷酸酯配体（P-OP）稳定的铑配合物已经在苯乙烯，乙烯基萘和烯丙基氰化物的不对称加氢甲酰化中进行了测试。基于单晶X射线衍射分析和NMR研究，已发现受限的芳基旋转可表征配体1e和1f。铑催化的加氢甲酰化反应的结果高度取决于膦-亚磷酸酯和配体主链的两个配位功能的性质。在所研究的配体中，具有氧亚苯基主链和PAr 2末端的配体产生了最佳结果，优于具有P的那些。-立体生成的膦基。1-萘基取代的催化剂使苯乙烯以71％ee的氢甲酰化，而二甲苯基催化剂在烯丙基氰化物的加氢甲酰化方面提供了最佳结果，在支链异构体中ee的iso / n比为13和53％ 。通过使Rh（acac）（CO）2反应生成了几种式为RhH（CO）2（P-OP）的氢化（羰基）物质/ P-OP与合成气。原位高压NMR实验表明，膦基占据了三角双锥体配位几何结构的顶端位置，在乙烯基芳烃的加氢甲酰化过程中，膦取代基与底物之
• Synthesis, Characterization, and Reactivity of Ruthenium Bis-Allyl Complexes with Chiral Phosphine-Phosphite Ligands
  作者：Mónica Vaquero、Sergio Vargas、Andrés Suárez、Sergio E. Garcı́a-Garrido、Eleuterio Álvarez、Manuel Mancera、Antonio Pizzano

  DOI：10.1021/om300018s

  日期：2012.5.14

  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.
• Iridium Complexes with Phosphine−Phosphite Ligands. Structural Aspects and Application in the Catalytic Asymmetric Hydrogenation of N-Aryl Imines
  作者：Sergio Vargas、Miguel Rubio、Andrés Suárez、Diego del Río、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1021/om050885t

  日期：2006.2.1

  A family of modularly designed phosphine-phosphites (P-OP), possessing a C-C-O backbone, has been synthesized and evaluated in the iridium-catalyzed asymmetric hydrogenation of N-aryl imines. The enantioselectivity of this reaction is highly dependent on the nature of the ligand, and catalysts bridged by an oxyethylene fragment have produced significantly higher enantiomeric excesses (Delta ee > 20%) than their o-oxyphenylene counterparts. Structural studies by X-ray crystallography and NMR spectroscopy of complexes with the formulation [Ir(COD)(P-OP)]BF4 and Ir(Cl)(CO)(P-OP), complemented by DFT calculations of model compounds of the chlorocarbonyls, have shown important differences between complexes bridged by an aliphatic or an aromatic bridge, regarding the iridacycle conformation and the location of phosphine substiments. Catalyst optimization has afforded enantioselectivities from 72 to 85% ee in the hydrogenation of several N-aryl imines.