[2-(4,8-ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-diphenylphosphane | 412050-20-5

• 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]-diphenylphosphane
• CAS: 412050-20-5
• 化学式: C₄₂H₄₆O₃P₂
• 分子量: 660.773
• InChiKey: DJPBOKDFAGUSHW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.7
• 重原子数：
  47
• 可旋转键数：
  7
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.29
• 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：

  双(乙腈)氯化钯(II) 、 [2-(4,8-ditert-butyl-1,2,10,11-tetramethylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxyphenyl]-diphenylphosphane 以 甲苯 为溶剂， 以60%的产率得到
  参考文献：
  名称：

  手性膦-亚磷酸酯配体修饰的Rh催化剂对烯烃的不对称加氢甲酰化作用

  摘要：

  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

  DOI：

  10.1021/om700744b
• 作为产物：
  描述：

  对茴香基二苯基膦 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]-diphenylphosphane
  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
• 作为试剂：
  描述：

  N-(8-methoxy-3,4-dihydronaphthalen-2-yl)acetamide 在 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]-diphenylphosphane 、 氢气 作用下， 以 二氯甲烷 为溶剂， 20.0 ℃ 、2.03 MPa 条件下， 反应 21.0h， 以83%的产率得到
  参考文献：
  名称：

  Rhodium Phosphine–Phosphite Catalysts in the Hydrogenation of Challenging N-(3,4-dihydronaphthalen-2-yl) Amide Derivatives

  摘要：

  The enantioselective catalytic hydrogenation of N-(3,4-dihydronaphthalen-2-yl) amides (1) with rhodium catalysts bearing phosphine-phosphite ligands 4 has been studied. A wide catalyst screening, facilitated by the modular structure of 4, has found a highly enantioselective catalyst for this reaction. This catalyst gives a 93% ee in the hydrogenation of la and also produces high enantioselectivities, ranging from 83 to 93% ee, in the hydrogenation of several OMe- and Br- substituted substrates. In contrast, the structurally related enol esters 2 are very reluctant to undergo hydrogenation. A coordination study of the representative enamide Id has shown an unusual eta(6)-arene coordination mode, over the typical O,C,C chelating mode for enamides, as the preferred one for this substrate in a Rh(I) complex. Deuteration reactions of 1c,d indicate a clean syn addition of deuterium to the double bond without an isotopic effect on the enantioselectivity.

  DOI：

  10.1021/jo400345v

文献信息

• Highly Enantioselective Imine Hydrogenation Catalyzed by Ruthenium Phosphane-Phosphite Diamine Complexes
  作者：Mónica Vaquero、Andrés Suárez、Sergio Vargas、Giovanni Bottari、Eleuterio Álvarez、Antonio Pizzano

  DOI：10.1002/chem.201203193

  日期：2012.12.3

  Mildly does it: A highly enantioselective catalyst for the hydrogenation of N‐aryl imines is described (see scheme). This catalyst offers practical advantages because it operates under very mild conditions and is based on an Ru complex with a diamine as the sole chiral ligand.

  轻度地做：描述了一种用于N-芳基亚胺氢化的高度对映选择性的催化剂（参见方案）。该催化剂具有实际优势，因为它在非常温和的条件下运行，并且基于Ru络合物，其中二胺是唯一的手性配体。
• Highly Enantioselective Hydrogenation of 1-Alkylvinyl Benzoates: A Simple, Nonenzymatic Access to Chiral 2-Alkanols
  作者：Patryk Kleman、Pedro J. González-Liste、Sergio E. García-Garrido、Victorio Cadierno、Antonio Pizzano

  DOI：10.1002/chem.201303500

  日期：2013.11.25

  Going chiral! Highly enantioselective catalytic hydrogenations of enol esters 1 by using a Rh catalyst bearing a POP ligand are described (see scheme; NBD=norbornadiene). The catalytic system has a broad scope and allows the preparation of a wide range of chiral esters 2 bearing diverse alkyls or a benzyl group with high enantioselectivities. These esters can easily be converted in highly enantioenriched

  走向手性！描述了通过使用带有P bearingOP配体的Rh催化剂对烯醇酯1的高度对映选择性催化氢化（参见方案； NBD ＝降冰片二烯）。该催化体系具有广泛的范围，并允许制备具有高对映选择性的各种带有各种烷基或苄基的手性酯2。这些酯可以很容易地转化为高度对映体富集的2-链烷醇。
• 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
• 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.