diphenethyl(phenyl)phosphine | 78722-77-7

• 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: diphenethyl(phenyl)phosphine
• 英文别名: Phenyl-bis(2-phenylethyl)phosphane
• CAS: 78722-77-7
• 化学式: C₂₂H₂₃P
• 分子量: 318.398
• InChiKey: ZMWUFUWOZJZVGD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 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：

  iron(dichloride)*1.5(tetrahydrofuran) 、 diphenethyl(phenyl)phosphine 以 四氢呋喃 为溶剂， 以65%的产率得到
  参考文献：
  名称：

  两种高活性，空气稳定的铁（III）-μ-氧代预催化剂的研究：使用苯基和二苯基膦进行氢磷酸化的合成范围

  摘要：

  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。

  DOI：

  10.1002/adsc.201501179
• 作为产物：
  描述：

  苯乙烯 在 C₃₁H₆₀N₂O₅Si₂Yb 作用下， 以 氘代苯 为溶剂， 反应 5.0h， 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

文献信息

• Versatile Visible‐Light‐Driven Synthesis of Asymmetrical Phosphines and Phosphonium Salts
  作者：Percia Beatrice Arockiam、Ulrich Lennert、Christina Graf、Robin Rothfelder、Daniel J. Scott、Tillmann G. Fischer、Kirsten Zeitler、Robert Wolf

  DOI：10.1002/chem.202002646

  日期：2020.12.9

  Asymmetrically substituted tertiary phosphines and quaternary phosphonium salts are used extensively in applications throughout industry and academia. Despite their significance, classical methods to synthesize such compounds often demand either harsh reaction conditions, prefunctionalization of starting materials, highly sensitive organometallic reagents, or expensive transition‐metal catalysts. Mild

  不对称取代的叔膦和季鏻盐广泛应用于工业界和学术界。尽管它们很重要，但合成此类化合物的经典方法通常需要苛刻的反应条件、起始材料的预官能化、高度敏感的有机金属试剂或昂贵的过渡金属催化剂。因此，尽管目前人们很感兴趣，但温和、实用的方法仍然难以捉摸。在这里，我们描述了一种可见光驱动的方法，由仲膦和伯膦形成这些产品。使用廉价的有机光催化剂和蓝光照射，芳基膦可以使用市售的有机卤化物进行烷基化和芳基化。此外，相同的有机催化剂可用于在单个反应步骤中将白磷（P 4 ）直接转化为对称芳基膦和鏻盐，这在以前只能使用贵金属催化来实现。
• 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）。
• Metallacyclic yttrium alkyl and hydrido complexes: synthesis, structures and catalytic activity in intermolecular olefin hydrophosphination and hydroamination
  作者：Alexander A. Kissel、Tatyana V. Mahrova、Dmitry M. Lyubov、Anton V. Cherkasov、Georgy K. Fukin、Alexander A. Trifonov、Iker Del Rosal、Laurent Maron

  DOI：10.1039/c5dt00129c

  日期：——

  the acidity of the metal center in the complex that is partially overcome by a better donation from the double bond (better overlap with an empty d orbital at the yttrium center). The treatment of complex 4 with DME resulted in the C–O bond cleavage of DME and afforded a three nuclear methoxide oxide complex [[L1]Y}3(μ2-OMe)3(μ3-O)]2−[Li(DME)3]+2 (6). Complexes 2, 3, 5 and 7 proved to be efficient precatalysts

  金属双环中性和离子钇烷基络合物，由双价烯-二酰胺配体配位[[2,6-iPr 2 C 6 H 3 NC（Me）C（Me）NC 6 H 3 iPr 2 -2,6] = L 1） [L 1 ] Y（CH 2 SiMe 3）（THF）2（2），[L 1 ] Y（CH 2 SiMe 3）2 } - Li（THF）4 } +（3），[L 1 ] Y（OEt 2）（μ-Me）2从相关的氯配合物[L 1 ] Y（THF）2（μ-Cl）2 Li（THF）2（1）分别在70、85和72中使用盐复分解法合成Li（TMEDA）（4）％收率分别。2与H 2或PhSiH 3的反应提供二聚体氢化物[L 1 ] Y（THF）（μ-H）} 2（μ-THF）（5），其中包含两个μ-桥氢化基和一个μ-桥THF配体（91％和85％的产率）。复合物的X射线研究2，3和5揭示η 2作为C -coordination烯-二酰胺配
• Amido Ca and Yb(II) Complexes Coordinated by Amidine-Amidopyridinate Ligands for Catalytic Intermolecular Olefin Hydrophosphination
  作者：Ivan V. Lapshin、Olga S. Yurova、Ivan V. Basalov、Vasily Yu. Rad’kov、Elvira I. Musina、Anton V. Cherkasov、Georgy K. Fukin、Andrei A. Karasik、Alexander A. Trifonov

  DOI：10.1021/acs.inorgchem.8b00088

  日期：2018.3.5

  A series of amido Ca and Yb(II) complexes LM[N(SiMe3)2](THF) (1Yb, 1–4Ca) coordinated by amidine-amidopyridinate ligands L1–4 were synthesized via a transamination reaction between proligands L1–4H and bisamido complexes M[N(SiMe3)2]2(THF)2 (M = Yb, Ca). The reactions of Yb[N(SiMe3)2]2(THF)2 with proligands L2H-L4H containing CF3 and C6H4F fragments do not allow for preparing the target Yb(II) complexes

  一系列酰氨钙和Yb的（II）配合物LM [N（森达3）2 ]（THF）（1YB，1-4Ca）通过脒amidopyridinate协调配体大号1 - 4分别经由前配体之间的转氨基反应合成大号1 – 4 H和双酰胺基配合物M [N（SiMe 3）2 ] 2（THF）2（M = Yb，Ca）。Yb [N（SiMe 3）2 ] 2（THF）2与配体L 2 H - L的反应4 ħ含有CF 3和C 6 H ^ 4 ˚F片段不允许用于制备目标镱（II）配合物，而钙类似物被以良好的收率合成。络合物1YB和1 - 4CA评价为预催化剂用于苯乙烯的hydrophosphination， p -取代的苯乙烯，α-ME-苯乙烯，和2,3-二甲基与各种伯和仲膦（PhPH 2，2,4,6--ME 3 C 6 H 2 PH 2，2 -C 5 NH 4 PH 2，Ph 2 PH，Cy2 PH）。络合物1YB，1 - 4C