二苯基(吡啶-2-基甲基)膦 | 20174-01-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 中文名称: 二苯基(吡啶-2-基甲基)膦
• 英文名称: 2-diphenylphosphinomethylpyridine
• 英文别名: 2-((Diphenylphosphanyl)methyl)pyridine；diphenyl(pyridin-2-ylmethyl)phosphane
• CAS: 20174-01-0
• 化学式: C₁₈H₁₆NP
• 分子量: 277.305
• InChiKey: HSPPMGREDUAMES-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.06
• 拓扑面积：
  12.9
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  二苯基(吡啶-2-基甲基)膦 在 双氧水 作用下， 以 丙酮 为溶剂， 反应 1.0h， 生成 Diphenyl-2-pyridylmethyl-phosphinoxid
  参考文献：
  名称：

  Syntheses and coordination chemistry of methylpyridylphosphine oxide ligands with copper(II)

  摘要：

  The coordination properties of three heterofunctional phosphine oxide ligands, 2-methylpyridyldiphenylphosphine oxide (L1), phenylphosphino-bis-2-methylpyridine oxide (L2) and phenylphosphino-bis-2-methylpyridine N,N',P-trioxide (L3) with Cu(II) is described. The X-ray crystal structures of the compounds display a distorted octahedral geometry, which exhibit Jahn-Teller distortions. In compounds 1 and 2, the L1 and 12 ligands react with Cu(BF4)(2) in a 2:1 ligand to metal ratio, respectively, with the BF4 anions interacting with the metal center. L3 reacts with Cu(BF4)(2) in 1:1 and 2:1 ligand/metal ratios to form compounds 3 and 4, respectively. Addition of either 2,2'-bipyridine or 4,4'-bipyridine to reaction solutions containing Cu(BF4)(2) and U produces a discrete molecule (5) and a polymeric structure (7), respectively. The reaction of both bipyridines in the presence of Cu(BF4)(2) and L3 gives rise to a discrete molecule (6) characterized by two octahedral coppers interconnected by the 4,4'-bipyridine. The electrochemical and photophysical properties of all compounds were investigated by cyclic voltammetry (CV) and UV-Vis, as they exhibited no emission or excitation in fluorimetric experiments. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2010.02.019
• 作为产物：
  描述：

  2-(diphenylphosphinomethyl)pyridine hydrochloride 在 碳酸氢钠 作用下， 以 二氯甲烷 、 水 为溶剂， 以99%的产率得到二苯基(吡啶-2-基甲基)膦
  参考文献：
  名称：

  Rhodium-Catalyzed Addition of Carboxylic Acids to Terminal Alkynes towards Z-Enol Esters

  摘要：

  Caution! A protection shield should be placed in front of the reaction set-up used for the preparation of (Z)-1-benzoyloxy)-1-octene.

  DOI：

  10.15227/orgsyn.093.0367
• 作为试剂：
  描述：

  1-辛炔 、 2,4,6-三甲氧基苯甲酸 在 chloro(1,5-cyclooctadiene)rhodium(I) dimer 、 二苯基(吡啶-2-基甲基)膦 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 以88%的产率得到(Z)-1-(2,4,6-trimethoxybenzoyloxy)-1-octene
  参考文献：
  名称：

  铑催化炔烃中羧酸的选择性抗马尔科夫尼科夫加成反应

  摘要：

  在铑催化的条件下，首次实现了将羧酸选择性地分子间反Markovnikov加成到末端炔烃上，从而生成有价值的Z-烯醇酯。该催化剂体系适用于广泛的底物范围并显示出广泛的官能团耐受性。

  DOI：

  10.1021/ol102365e

文献信息

• Hydrogenation of Carbonyl Derivatives Catalysed by Manganese Complexes Bearing Bidentate Pyridinyl-Phosphine Ligands
  作者：Duo Wei、Antoine Bruneau-Voisine、Téo Chauvin、Vincent Dorcet、Thierry Roisnel、Dmitry A. Valyaev、Noël Lugan、Jean-Baptiste Sortais

  DOI：10.1002/adsc.201701115

  日期：2018.2.15

  Manganese(I) catalysts incorporating readily available bidentate 2‐aminopyridinyl‐phosphine ligands achieve a high efficiency in the hydrogenation of carbonyl compounds, significantly better than parent ones based on more elaborated and expensive tridentate 2,6‐(diaminopyridinyl)‐diphosphine ligands. The reaction proceeds with low catalyst loading (0.5 mol%) under mild conditions (50 °C) with yields

  结合了易于使用的二齿2-氨基吡啶基-膦配体的锰（I）催化剂在羰基化合物的加氢方面实现了高效率，明显优于基于更精细和昂贵的三齿2,6-（二氨基吡啶基）-二膦基配体的母体。在温和条件下（50°C），反应以低催化剂负载量（0.5 mol％）进行，收率高达96％。
• Conformational twisting of a formate-bridged diiridium complex enables catalytic formic acid dehydrogenation
  作者：Paul J. Lauridsen、Zhiyao Lu、Jeff J. A. Celaje、Elyse A. Kedzie、Travis J. Williams

  DOI：10.1039/c8dt03268h

  日期：——

  iridium complex 1a enables the first homogeneous catalytic dehydrogenation of neat formic acid and enjoys unusual stability through millions of turnovers. Binuclear iridium hydride species 5a, which features a provocative C2-symmetric geometry, was isolated from the reaction as a catalyst resting state. By synthesizing and carefully examining the catalytic initiation of a series of analogues to 1a,

  我们之前报道过，铱配合物1a首次实现了纯甲酸的均相催化脱氢，并在数百万次的转换中具有异常的稳定性。双核氢化铱物质5a具有激发性的C 2对称几何形状，作为催化剂静止状态从反应中分离出来。通过合成并仔细检查一系列 1a 类似物的催化引发，我们在此建立了类似于5a的 C2 扭曲铱二聚体的形成与甲酸脱氢反应性之间的强相关性：有效的 C2 扭曲似乎是1a所独有的对催化反应至关重要。
• Development of an Improved Rhodium Catalyst for<i>Z</i>-Selective Anti-Markovnikov Addition of Carboxylic Acids to Terminal Alkynes
  作者：Siping Wei、Julia Pedroni、Antje Meißner、Alexandre Lumbroso、Hans-Joachim Drexler、Detlef Heller、Bernhard Breit

  DOI：10.1002/chem.201300160

  日期：2013.9.2

  To develop more active catalysts for the rhodium‐catalyzed addition of carboxylic acids to terminal alkynes furnishing anti‐Markovnikov Z enol esters, a thorough study of the rhodium complexes involved was performed. A number of rhodium complexes were characterized by NMR, ESI‐MS, and X‐ray analysis and applied as catalysts for the title reaction. The systematic investigations revealed that the presence

  为了开发更多的活性催化剂，以铑催化向末端炔烃中提供羧酸，以提供抗马尔科夫尼科夫Z烯醇酯，我们对所涉及的铑配合物进行了深入研究。通过NMR，ESI-MS和X射线分析对许多铑配合物进行了表征，并用作标题反应的催化剂。系统研究表明，氯离子的存在降低了催化剂的活性。相反，产生和应用两种铑种，即，铑[Rh（DPPMP）的混合物2 ] [H（苯甲酸酯）2 ]（DPPMP = diphenylphosphinomethylpyridine）和[的Rh（COD）（μ 2 -苯甲酸甲酯）} 2]，提供了明显更活泼的催化剂。此外，添加催化量的碱（Cs 2 CO 3）具有额外的促进作用。较高的催化剂活性使反应时间从16小时减少至1-4小时，同时保持了较高的选择性。对底物范围的研究表明，新型催化剂具有更大的官能团相容性。
• P∧N versus N∧N ligands for the palladium-catalyzed alternating copolymerization of styrene and carbon monoxide
  作者：Anton Aeby、Giambattista Consiglio

  DOI：10.1016/s0020-1693(99)00302-3

  日期：1999.12

  modified by C1-symmetric chelate ligands containing the 3-phenyl-4-methoxymethyl-4,5-dihydrooxazole chiral moiety and either 2-pyridyl or 2-diphenylphosphinophenyl substituents, catalyze the copolymerization of styrene with carbon monoxide with either a prevailingly syndiotactic or isotactic microstructure, respectively. This and other results obtained with several ligands are interpreted on the basis

  阳离子钯（II）配合物，由含有3-苯基-4-甲氧基甲基-4,5-二氢恶唑手性部分和2-吡啶基或2-二苯基膦基苯基取代基的C1对称螯合配体修饰，催化苯乙烯与一氧化碳的共聚具有主要为间同或等规的微观结构。用几种配体获得的该结果和其他结果是基于在迁移插入引起链增长之前烯烃的位点选择性配位来解释的。
• Bis(perchlorocatecholato)silane and heteroleptic bidonors: hidden frustrated Lewis pairs resulting from ring strain
  作者：Deborah Hartmann、Sven Braner、Lutz Greb

  DOI：10.1039/d1cc03452a

  日期：——

  Bis(perchlorocatecholato)silane and bidentate N,N- or N,P-heteroleptic donors were reacted to form hexacoordinated complexes. Depending on the ring strain and hemilability in the adducts, frustrated Lewis pair (FLP) reactivity with aldehydes and catalytic ammonia borane dehydrocoupling was enabled. All reactions were analyzed using density functional theory. This approach represents an alternative

  双（全氯儿茶酚）硅烷和双齿N , N - 或N , P -杂配供体反应形成六配位配合物。根据加合物中的环应变和半化率，可以抑制路易斯对 (FLP) 与醛的反应和催化氨硼烷脱氢偶联。使用密度泛函理论分析所有反应。这种方法代表了一种替代方法，除了依赖空间体积之外，还可以在双分子 FLP 中实现挫败。