(2-cyclohexylphenyl)dicyclohexylphosphine | 625856-27-1

• 物质功能分类: 有机原料 - 有机膦化合物
• 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-cyclohexylphenyl)dicyclohexylphosphine
• 英文别名: bis(2-cyclohexylphenyl)dicyclohexylphosphane；Dicyclohexyl(2-cyclohexylphenyl)phosphane；dicyclohexyl-(2-cyclohexylphenyl)phosphane
• CAS: 625856-27-1
• 化学式: C₂₄H₃₇P
• 分子量: 356.532
• InChiKey: PBWQTYUASDMXLB-UHFFFAOYSA-N

物化性质

• 沸点：
  476.4±24.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  7.6
• 重原子数：
  25
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  (2-cyclohexylphenyl)dicyclohexylphosphine 在 氧气 作用下， 以 甲苯 为溶剂， 生成 1-Cyclohexyl-2-dicyclohexylphosphorylbenzene
  参考文献：
  名称：

  Rationale Behind the Resistance of Dialkylbiaryl Phosphines toward Oxidation by Molecular Oxygen

  摘要：

  Electron-rich dialkylbiaryl phosphines, which comprise a common class of supporting ligands for Pd-catalyzed cross-coupling reactions, are highly resistant toward oxidation by molecular oxygen. Presented herein are possible reasons why this class of phosphine ligands manifests this property. Experimental and theoretical data suggest that the two alkyl substituents on the phosphorus center and the 2' and 6' positions of the biaryl backbone play an important role in inhibiting oxidation of this class of ligands.

  DOI：

  10.1021/ja0683180

文献信息

• Au⋅⋅⋅H−C Hydrogen Bonds as Design Principle in Gold(I) Catalysis
  作者：Heidar Darmandeh、Julian Löffler、Nikolaos V. Tzouras、Busra Dereli、Thorsten Scherpf、Kai‐Stephan Feichtner、Sofie Vanden Broeck、Kristof Van Hecke、Marina Saab、Catherine S. J. Cazin、Luigi Cavallo、Steven P. Nolan、Viktoria H. Gessner

  DOI：10.1002/anie.202108581

  日期：2021.9.13

  Secondary ligand–metal interactions are decisive in many catalytic transformations. While arene–gold interactions have repeatedly been reported as critical structural feature in many high-performance gold catalysts, we herein report that these interactions can also be replaced by Au⋅⋅⋅H−C hydrogen bonds without suffering any reduction in catalytic performance. Systematic experimental and computational

  次级配体-金属相互作用在许多催化转化中起决定性作用。虽然芳烃-金相互作用已被多次报道为许多高性能金催化剂的关键结构特征，但我们在此报告这些相互作用也可以被 Au⋅⋅⋅H−C 氢键取代，而不会降低催化性能。对一系列具有 PPh 3 ( Ph YPhos) 或 PCy 3 ( Cy YPhos) 部分的叶立德取代膦进行的系统实验和计算研究表明，芳基取代化合物中的芳烃-金相互作用可以通过形成Au⋅⋅⋅H−C 氢键。最强的相互作用是与鎓中心旁边的 C−H 部分发现的，由于极化导致与迄今为止报道的最短的 Au⋅⋅⋅H−C 氢键产生非常强的相互作用。对金配合物形成的量热研究进一步证实Ph YPhos 和Cy YPhos 配体形成类似的稳定配合物。因此，两种配体在炔烃的加氢胺化、加氢苯氧基化和加氢羧化中表现出相同的催化性能，从而证明Au⋅⋅⋅H−C氢键比金-芳烃相互作用同样适合生成高效的金催化剂。通过联
• Synthesis of new o-alkyl substituted arylalkylphosphanes: study of their molecular structure and influence on rhodium-catalyzed propene and 1-hexene hydroformylation
  作者：Helena Riihimäki、Teija Kangas、Pekka Suomalainen、Heidi K Reinius、Sirpa Jääskeläinen、Matti Haukka、A.O.I Krause、Tapani A Pakkanen、Jouni T Pursiainen

  DOI：10.1016/s1381-1169(03)00026-8

  日期：2003.6

  of new phosphane ligands designed to increase the branched-to-normal ratio of the hydroformylation reaction were prepared in the same way as the previously reported ortho-alkyl substituted arylphosphanes, which have shown increased i/n ratios in the hydroformylation of propene and 1-hexene. In order to determine the relationship between the catalytic behavior and stereoelectronic properties of the

  以与先前报道的邻烷基取代的芳基膦相同的方式，制备了一组设计用于增加加氢甲酰化反应的支链-正态比的新膦配体，后者在丙烯和甲酰胺的加氢甲酰化中显示出增加的i / n比。 1-己烯。为了确定配体的催化行为与立体电子性质之间的关系，将各种官能烷基（甲基，异丙基，环己基）直接置于磷原子上，并置于与磷连接的苯环的邻位。在丙烯和1-己烯的加氢甲酰化反应中，较高的i / n与三苯基膦相比，几乎所有配体的比率都得到了提高。另外，随着邻烷基取代基变大，它对i-选择性具有有利的影响。配体的表征通过NMR光谱进行（主要是， }， }，HSQC / HETCOR和COZY-90）。还通过量子力学计算和合成三种Rh（aCAC）（CO）（PR 3）衍生物研究了配体的性质。所述ø -烷基取代基被取向在（2-己基苯基）二环己基膦和（2,5-二甲基苯基）的X射线晶体结构的配位体的锥角之外的双（4-吡啶基）膦，和Rh（ACAC）（一氧化碳）（PR
• Correlation of Experimental and Calculated Reaction Enthalpies with Ligand Donor Strengths
  作者：Julian Löffler、Sofie M. P. Vanden Broeck、Catherine S. J. Cazin、Steven P. Nolan、Viktoria H. Däschlein-Gessner

  DOI：10.1002/chem.202300151

  日期：——

  Calorimetric studies on the formation of [(YPhos)AuCl] complexes confirmed the high binding strength of these ligands. The reaction enthalpies are shown to be easily obtained by calculations and correlate with the phosphine donor properties thus representing an interesting problem-specific descriptor for ligands in gold catalysis.

  [(YPhos)AuCl] 复合物形成的量热研究证实了这些配体的高结合强度。反应焓显示很容易通过计算获得，并与膦供体特性相关，因此代表了金催化中配体的一个有趣的特定问题描述符。
• Effective new palladium catalysts for the Suzuki coupling of various haloxylenes to prepare sterically hindered bi- and triaryls
  作者：Sauli Vuoti、Juho Autio、M. Haukka、J. Pursiainen

  DOI：10.1016/j.ica.2009.06.032

  日期：2009.10

  Several new ortho-alkyl and heteroalkyl substituted aryl and aryl alkyl phosphanes and their palladium complexes have been selectively prepared, characterized and compared as potential catalysts for the Suzuki coupling reaction. The modification of the structures of the palladium complexes were made in search of the best possible catalytic activity. The novel catalysts were subsequently used to synthesize sterically hindered bi- and triaryls by coupling various bulky, unactivated bromoxylenes and chloroxylenes with a range of phenyl boronic acids under microwave irradiation. We showed that under optimized reaction conditions, very good results can be obtained with a selection of the new phosphanes and their mononuclear palladium complexes. (C) 2009 Elsevier B. V. All rights reserved.