phenethyl(phenyl)phosphine | 152076-26-1

• 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: phenethyl(phenyl)phosphine
• 英文别名: Benzylmethylphenylphosphine；phenyl(2-phenylethyl)phosphane
• CAS: 152076-26-1
• 化学式: C₁₄H₁₅P
• 分子量: 214.247
• InChiKey: IDYVIRRMXMJBIG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  15.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.14
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  苯乙烯 、 phenethyl(phenyl)phosphine 在 C₃₁H₆₀N₂O₅Si₂Yb 作用下， 以 氘代苯 为溶剂， 反应 3.0h， 生成 diphenethyl(phenyl)phosphine
  参考文献：
  名称：

  二价稀土和碱土金属的氨基醚-酚醛预催化剂对活化烯烃的一次和二次加氢磷酸化作用

  摘要：

  A range of stable ytterbium(II) amino ether-phenolato amido complexes of the type {LONxOy}Yb{N(SiMe3)(2)}, together with a congeneric samarium(II) and two calcium and strontium amido and alkyl derivatives, have been synthesized. They constitute very active, fully regioselective (anti-Markovnikov), and chemoselective precatalysts for the intermolecular hydrophosphination of styrene derivatives with PhPH2, achieving TONs up to 2150, TOFs up to 30 h(-1) and chemoselectivities in the region of 95-99%. The ytterbium(II) precatalysts, among which is most prominently {LONO4}Yb{N(SiMe3)(2)} (3), where the ligand possesses a 15-c-5-aza-crown ether side arm, outperform their related calcium analogues, and the activity of the catalyst increases substantially with the denticity of the ligand. The rate law rate = k[p-Bu-t-styrene] [3] was established, following kinetic monitoring of the hydrophosphination of p-Bu-t-styrene and PhPH2 catalyzed by 3. The kinetic studies also revealed that the reactions are entropically driven and that reaction rates increase when electron-withdrawing groups are introduced at the Para position of the styrenic substrate. It is proposed that these catalyzed hydrophosphination reactions proceed by rate-limiting olefin insertion into the [Yb] phosphide bond. The chemoselective one-pot, two-step double hydrophosphination of PhPH2 with 2 equiv of styrene yields tertiary phosphines. It obeys an unusual kinetic profile where formation of the tertiary phosphine starts only when complete consumption of PhPH2 is first ensured. This sequence was used to obtain asymmetric tertiary phosphines with excellent selectivity.

  DOI：

  10.1021/acs.organomet.6b00252
• 作为产物：
  描述：

  Phosphorodichloridous acid, 2-phenylethyl ester 在 苯硅烷 、 异丙基氯化镁 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 1.5h， 生成 phenethyl(phenyl)phosphine
  参考文献：
  名称：

  未活化炔烃的镍催化不对称氢膦化反应

  摘要：

  P-立体叔膦的实际合成在不对称催化、材料和药物化学中具有广泛的应用，是一项重大挑战。设计了一种由镍配合物催化的廉价和普遍存在的炔烃的区域和对映选择性氢膦化反应，其中原位制备了有毒和空气敏感的二级膦来自工作台稳定的二级氧化膦。这种方法已被证明具有前所未有的底物范围和官能团兼容性，可提供电子和结构多样化的 P(III) 化合物。这些产物可以很容易地转化为双齿配体和有机催化剂的各种前体，以及各种包含P和金属立体中心的过渡金属配合物。

  DOI：

  10.1021/jacs.1c05649

文献信息

• Barium complexes with crown-ether-functionalised amidinate and iminoanilide ligands for the hydrophosphination of vinylarenes
  作者：Erwann Le Coz、Hanieh Roueindeji、Thierry Roisnel、Vincent Dorcet、Jean-François Carpentier、Yann Sarazin

  DOI：10.1039/c9dt01512d

  日期：——

  The detailed multistep syntheses of two nitrogen-based sterically congested iminoanilidine and amidine proligands bearing a tethered 15-member aza-ether-crown macrocycle, namely I^Acrown}H and Amcrown}H, are reported. These proligands react with [BaN(SiMe2H)2}2·(thf)n] to generate the heteroleptic barium complexes [I^Acrown}BaN(SiMe2H)2] (5) and [Amcrown}BaN(SiMe2H)2] (6) in high yields. These

  据报道，带有氮系的15元氮杂-醚-冠状大环，即I ^ A冠} H和Am冠} H的两个基于氮的空间拥挤的亚氨基丙啶和and pro配体的详细的多步合成方法。这些配体与[Ba N（SiMe 2 H）2 } 2 ·（thf）n ]反应生成杂合钡络合物[I ^ A Crown } BaN（SiMe 2 H）2 ]（5）和[Am冠} BaN（SiMe 2 H）2 ]（6）高产。这些配合物表现出很高的配位数（分别为8和7），并通过轻度的Ba⋯H-Si相互作用而稳定。异常地为亲氧性元件，诸如钡，在脒基配体6仅η 1配位的。配合物5和6介导苯乙烯与伯（PhPH 2）和仲（HPPh 2）膦的分子间加氢磷酸化。在这些反应中，它们的催化性能优于其他钡预催化剂。在5催化的HPPh 2催化的苯乙烯氢磷酸化过程中，磷络合物[I ^ A Crown } BaPPh2 ]（ 7）可被截取并进行晶体学表征。
• Ln(<scp>ii</scp>) amido complexes coordinated by ring-expanded N-heterocyclic carbenes – promising catalysts for olefin hydrophosphination
  作者：Ivan V. Lapshin、Anton V. Cherkasov、Andrey F. Asachenko、Alexander A. Trifonov

  DOI：10.1039/d0cc05424k

  日期：——

  First Ln(II) ring-expanded NHC complexes (er-NHC)Ln[N(SiMe3)2]2 (Ln = Sm, Yb) are synthesized and proved to be highly efficient pre-catalysts for the intermolecular hydrophosphination of such indolent substrates as 1-alkenes, cyclohexene and norbornene.

  首先合成了Ln（II）环扩展的NHC络合物（er-NHC）Ln [N（SiMe 3）2 ] 2（Ln = Sm，Yb），并证明是这种惰性分子间氢磷酸化的高效预催化剂。底物为1-烯烃，环己烯和降冰片烯。
• Highly Active, Chemo- and Regioselective Yb^IIand Sm^IICatalysts for the Hydrophosphination of Styrene with Phenylphosphine
  作者：Ivan V. Basalov、Vincent Dorcet、Georgy K. Fukin、Jean-François Carpentier、Yann Sarazin、Alexander A. Trifonov

  DOI：10.1002/chem.201500380

  日期：2015.4.13

  aminoether–phenolate ligands and devoid of coordinated solvent have been structurally characterized. They afford highly active, chemoselective and, in the case of monoadditions, 100 % anti‐Markovnikov regiospecific catalysts (down to 0.04 mol % loading) for the hydrophosphination of styrene with PhPH2 under mild conditions.

  稳定的杂氨基酰胺Yb II和Sm II配合物带有氨基醚-酚盐配体，并且没有配位溶剂。它们提供了高活性，化学选择性，在单加成反应的情况下，可以在温和条件下用PhPH 2进行苯乙烯的氢磷酸化反应，使用100％抗马尔科夫尼科夫区域特异性催化剂（低至0.04 mol％负载）。
• A bench-stable copper photocatalyst for the rapid hydrophosphination of activated and unactivated alkenes
  作者：Steven G. Dannenberg、Rory Waterman

  DOI：10.1039/d0cc06570f

  日期：——

  that have never before been reported with an air-stable catalyst or at ambient temperature. The commercial availability, ease of use, and broad substrate scope of compound 1 make hydrophosphination more available to synthetic chemists.

  Cu（acac）2（1）是用于烯烃加氢磷酸化的高活性催化剂。光催化条件很关键，并且可以用空气稳定的催化剂或在环境温度下从未报道过的未活化的底物提供高转化率。化合物1的商业可得性，易用性和广泛的底物范围使加氢磷酸化更易于合成化学家使用。
• A Study of Two Highly Active, Air-Stable Iron(III)-μ-Oxo Precatalysts: Synthetic Scope of Hydrophosphination using Phenyl- and Diphenylphosphine
  作者：Kimberley J. Gallagher、Maialen Espinal-Viguri、Mary F. Mahon、Ruth L. Webster

  DOI：10.1002/adsc.201501179

  日期：2016.7.28

  The importance of phosphines in synthetic chemistry cannot be underestimated. Catalytic hydrophosphination offers an ideal method to prepare P−C bonds without the need for harsh reaction conditions or stoichiometric amounts of waste by‐product. We herein report our studies into two biocompatible iron(III) complexes in hydrophosphination chemistry using diphenylphosphine under mild and benign reaction

  膦在合成化学中的重要性不可低估。催化加氢磷酸化提供了制备P-C键的理想方法，而无需苛刻的反应条件或化学计量的废物副产物。我们在此报告了我们在温和和良性反应条件（室温，无溶剂）下使用二苯膦在氢磷化化学中对两种生物相容的铁（III）配合物的研究，以及我们对苯膦进行氢磷化的扩展探索，可以将其调整为在不存在的情况下运行在热条件下进行单加氢磷化或在无溶剂的情况下使用铁（III）预催化剂生成双加氢磷化产物的催化剂。