(cyclohexyl)2PCH2CH2PPh2 | 122425-32-5

• 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: (cyclohexyl)2PCH2CH2PPh2
• 英文别名: Ph2PCH2CH2PCy2；PCy2CH2CH2PPh2；cppe；Cy2PCH2CH2PPh2；Dicyclohexyl(2-diphenylphosphanylethyl)phosphane
• CAS: 122425-32-5
• 化学式: C₂₆H₃₆P₂
• 分子量: 410.519
• InChiKey: PNIBBYPVWCKCAO-UHFFFAOYSA-N

物化性质

• 熔点：
  54 °C
• 沸点：
  240 °C(Press: 1.9 Torr)

计算性质

• 辛醇/水分配系数(LogP)：
  6.4
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.54
• 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：

  (cyclohexyl)2PCH2CH2PPh2 以 二氯甲烷 、 氘代甲醇 为溶剂， 生成 Pd(PCy2CH2CH2PPh2)((13)CH(C6D5)CH2C6D5)(1+)
  参考文献：
  名称：

  Palladium catalysed alkyne hydrogenation and oligomerisation: a parahydrogen based NMR investigation

  摘要：

  通过PHIP（对氢诱导极化）NMR研究探讨了膦配体在钯(II)-双膦-氢阳离子催化苯基乙炔氢化反应中的作用。使用的前体为Pd(LL′)(OTf)₂（1a-e）[LL′ = dcpe（PCy₂CH₂CH₂PCy₂），dppe，dppm，dppp，cppe（PCy₂CH₂CH₂PPh₂）]。检测到类型为[Pd(LL′)(CHPhCH2Ph)](OTf)（2和3）的烷基钯中间体，并证明其在氢化催化中发挥了积极作用。磁化转移实验揭示了来自2a（LL′ = dcpe）和连接异构体2e′（LL′ = cppe）烷基配体的α-H在NMR时间尺度上与反式stilbene之间的化学交换。已确定该转化的活化参数（ΔH≠和ΔS≠）。这些实验结合GC/MS数据表明，在甲醇中催化活性更强，顺序为：dcpe > cppe > dppp > dppe > dppm，相比之下在CD₂Cl₂中活性较低。所描述的五种膦配体系统的活性均低于基于bcope（其中bcope为(C₈H₁₄)PCH₂–CH₂P(C₈H₁₄)）和tbucope（其中tbucope为(C₈H₁₄)PC₆H₄CH₂P(tBu)₂）的系统。检测到顺-顺-1,2,3,4-四苯基-丁-1,3-二烯作为次要反应产物，同时Pd(LL′)(PhCH–CHPh–CPhCHPh)⁺（4）在炔烃二聚化步骤中也显示出作用。

  DOI：

  10.1039/b804162h
• 作为产物：
  描述：

  乙烯基二苯基膦 、 二环己基膦 在 甲基苯锂 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成 (cyclohexyl)2PCH2CH2PPh2
  参考文献：
  名称：

  Catalysis of Diels-Alder reactions by low oxidation state transition-metal Lewis acids: fact and fiction

  摘要：

  DOI：

  10.1021/ja00198a015

文献信息

• A New Synthetic Route to Unsymmetrical 1,2-Bis(phosphanyl)ethanes and 1,2-Arsanyl(phosphanyl)ethanes with and without a Stereogenic Center
  作者：Guido Fries、Justin Wolf、Matthias Pfeiffer、Dietmar Stalke、Helmut Werner

  DOI：10.1002/(sici)1521-3773(20000204)39:3<564::aid-anie564>3.0.co;2-s

  日期：2000.2.4

  A one-pot reaction affords unsymmetrical 1,2-bis(phosphanyl)ethanes 2 and 1,2-arsanyl(phosphanyl)ethanes 3 from the cyclic sulfate 1 in high yield. Similarly, chiral 1,2-bis(phosphanyl)ethanes and 1,3-bis(phosphanyl)propanes could be obtained in enantiomerically pure form. R, R'=alkyl, phenyl.

  一锅法反应以高收率从环状硫酸盐1得到不对称的1，2-双（膦酰基）乙烷2和1，2-芳基（膦酰基）乙烷3。类似地，可以以对映体纯的形式获得手性1，2-双（膦酰基）乙烷和1，3-双（膦酰基）丙烷。R，R′＝烷基，苯基。
• Six-Coordinate Ruthenium(II) Complexes Containing Unsymmetrical 1,2-Bis(phosphanyl)ethanes and 1-Arsanyl-2-phosphanylethanes as Ligands
  作者：Guido Fries、Kerstin Ilg、Matthias Pfeiffer、Dietmar Stalke、Helmut Werner

  DOI：10.1002/1099-0682(200012)2000:12<2597::aid-ejic2597>3.0.co;2-f

  日期：2000.12

  afforded the chelate compound [Ru(κ2-[F6]acac)2(κ2-iPr2PCH2CH2PPh2)], whereas treatment of 2 and 3 with pentachlorophenol gave the related, more labile complexes [Ru(κ2-O,Cl-OC6Cl5)2(κ2-R2PCH2CH2PPh2)] [R = iPr (6), Cy (7)]. Preparation of the parent bis(acac) compound [Ru(κ2-acac)2(κ2-iPr2PCH2CH2PPh2)] (8), which could not be obtained from 2 and acacH, was achieved by ligand exchange of 6 and acetylacetone

  双(η3-2-甲基烯丙基)钌(II)配合物[Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2PR2)] [R = iPr (2), Cy (3)] 由 cycloocta-1 制备,5-二烯衍生物 [Ru(η3-2-MeC3H4)2(η4-C8H12)] (1) 和不对称的 1,2-双（膦酰基）乙烷 Ph2PCH2CH2PR2。As,P 类似物 [Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2AstBu2)] (4) 通过相同的途径获得。2 与六氟乙酰丙酮反应得到螯合物 [Ru(κ2-[F6]acac)2(κ2-iPr2PCH2CH2PPh2)]，而用五氯苯酚处理 2 和 3 得到相关的、更不稳定的复合物 [Ru(κ2-O, Cl-OC6Cl5)2(κ2-R2PCH2CH2PPh2)] [R = iPr (6), Cy (7)]。不能从 2 和 acacH 获得的母体双
• A new route to achiral and chiral 1,2-bis(phosphino)ethanes, 1-arsino-2-phosphinoethanes, and 1,3-bis(phosphino)propanes and the molecular structure and catalytic activity of some rhodium(i) complexes derived thereof Dedicated to Professor Wolfdieter A. Schenk, a respected colleague and creative scientist, on the occasion of his 60th birthday.
  作者：Guido Fries、Justin Wolf、Kerstin Ilg、Bernhard Walfort、Dietmar Stalke、Helmut Werner

  DOI：10.1039/b401585a

  日期：——

  A series of unsymmetrical 1,2-bis(phosphino)ethanes R2PCH2CH2PR′2 (2a–d) and 1-arsino-2-phosphinoethanes R2AsCH2CH2PR′2 (3a–c) mainly with bulky substituents R and R′ were prepared from the cyclic sulfate 1 by stepwise cleavage of the carbon–oxygen bonds by LiPR2 and LiPR′2 or LiAsR2 and LiPR′2, respectively. Analogously, racemic mixtures of R2PCH2CH(Me)PPh2 (R = iPr 5a, Cy 5b) as well as the enantiomers (R)-5a, (R)-5b and (R)-tBu2PCH2CH(Me)PPh2 (R)-5c were obtained from the corresponding unsymmetrical cyclic sulfates 4 and (S)-4. On a similar route, the racemates of the 1,3-bis(phosphino)propanes R2PCH2CH2CH(Me)PPh2 (R = iPr 7, tBu 8), optically pure (R)-8 and (S,S)-iPr2PCH(Me)CH2CH(Me)PPh2 (S,S)-10 were prepared. The reaction of [RhCl(η4-C8H12)}2] with chelating ligands L–L, where L–L is R2PCH2P(men)2 (R = iPr, Ph; men = (1S,2R,5S)-menthyl), Cy2AsCH2P(men)2, or (R)-5a, (R)-5b, (R)-5c, (R)-8 and (S,S)-10, in the presence of AgPF6, gave the complexes [Rh(η4-C8H12)(L–L)]PF6 (12a–h) which were used as pre-catalysts in the hydrogenation of the methyl ester of α-acetamidocinnamic acid (ACM). Depending on L–L, the solvent, the temperature and the pressure of H2, optical yields of up to 69% ee were achieved. For two of the rhodium complexes, 12c and 12d, the molecular structures were determined by X-ray crystallography.

  一系列不对称的 1、通过 LiPR2 和 LiPR′2 或 LiAsR2 和 LiPR′2逐步裂解碳氧键，从环状硫酸盐 1 制备出了主要带有大取代基 R 和 R′的 1、2-双（膦）乙烷 R2PCH2C R′2 (2a-d)和 1-胂-2-膦乙烷 R2AsCH2C R′2 (3a-c)。同样，从相应的不对称环状硫酸盐 4 和 (S)-4 中得到了 R2PCH2CH(Me)PPh2 的外消旋混合物（R = iPr 5a、Cy 5b）以及对映体 (R)-5a、(R)-5b 和 (R)-tBu2PCH2CH(Me)PPh2 (R)-5c。按照类似的路线，制备了 1,3-双（膦）丙烷 R2PCH2CH2CH(Me)PPh2（R = iPr 7，tBu 8）的外消旋体、光学纯 (R)-8 和 (S,S)-iPr2PCH(Me)CH2CH(Me)PPh2 (S,S)-10。[RhCl(η4-C8H12)}2]与螯合配体 L-L 反应，其中 L-L 是 R2PCH2P(men)2 （R = iPr，Ph；men=(1S,2R,5S)-menthyl)、Cy2AsC (men)2 或 (R)-5a、(R)-5b、(R)-5c、(R)-8 和 (S,S)-10、得到了[Rh(η4- )(L-L)]PF6（12a-h）复合物，这些复合物被用作 α-乙酰胺肉桂酸（ACM）甲酯氢化反应的前催化剂。根据 L-L、溶剂、温度和 H2 压力的不同，光学产率可达 69% ee。通过 X 射线晶体学，确定了 12c 和 12d 这两种铑络合物的分子结构。
• Mononuclear Ruthenium and Hetero-Tetranuclear Ruthenium-Silver Complexes Containing the Unsymmetrical Bidentate Ligands R2P(CH2)nER′2 (n = 1, 2; E = P, As) as Chelating or Bridging Units
  作者：Guido Fries、Birgit Weberndörfer、Kerstin Ilg、Helmut Werner

  DOI：10.1002/1099-0682(200007)2000:7<1651::aid-ejic1651>3.0.co;2-2

  日期：2000.7