methylenebis(2,4,6-triisopropylphenylphosphine) | 159726-72-4

• 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: methylenebis(2,4,6-triisopropylphenylphosphine)
• 英文别名: IsHP(CH2)PHIs；[2,4,6-tri(propan-2-yl)phenyl]-[[2,4,6-tri(propan-2-yl)phenyl]phosphanylmethyl]phosphane
• CAS: 159726-72-4
• 化学式: C₃₁H₅₀P₂
• 分子量: 484.686
• InChiKey: FSUNEGNTFLMJFD-UHFFFAOYSA-N

物化性质

• 沸点：
  527.7±50.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  9.6
• 重原子数：
  33
• 可旋转键数：
  10
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.61
• 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：

  methylenebis(2,4,6-triisopropylphenylphosphine) 在 sodium trimethylsilanolate 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 [Pt(dppe)((2,4,6-(i-Pr)₃C₆H₂)PCH₂PMe(2,4,6-(i-Pr)₃C₆H₂))](triflate)
  参考文献：
  名称：

  Synthesis, Structure, Dynamics, and Selective Methylation of Platinum and Palladium Diphosphametallacyclobutane Complexes

  摘要：

  Treatment of M(dppe)Cl-2 (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)Cl-2 with IsHPCH(2)PHIs (1; Is = isityl = 2,4,6-(i-Pr)(3)C6H2) and 2 equiv of NaOSiMe3 gave the mononuclear diphosphametallacyclobutane complexes M(dppe)(IsPCH(2)PIs) (M = Pd (2), Pt (3)), or Pt((1,R)-Me-DuPhos)(IsPCH(2)PIs) (4). Dynamic processes involving phosphorus inversion and rotation about the P-C (1s) bonds in 2-4 were characterized by variable-temperature NMR spectroscopy, which suggested that each existed as a single C-2-symmetric diastereomer in solution, consistent with their solid-state structures determined by X-ray crystallography. The MiniPhos derivative IsMePCH(2)PMeIs (5) was prepared as a 5.5/1 rac/meso mixture by sequential arylation and methylation of Cl2PCH2PCl2. Alternatively, the catalyst precursor Pt((1,R)-Me-DuPhos)(Ph)(Cl) mediated alkylation of secondary phosphines in the presence of NaOSiMe3 to yield selectively meso-5 either from PHMe(1s) and CH2I2 or from 1 and MeI. Recrystallization and chromatography yielded diastereomerically enriched rac-5 and meso-5. Treatment of M(dppe)(OTf)(2) (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)(OTf)(2) with meso-5 gave the dications meso-[M(diphos)(IsMePCH(2)PMeIs)][OTf](2) (M(diphos) = Pd(dppe) (6), Pt(dppe) (8), Pt((R,R)-Me-DuPhos) (10)). Similar reactions of rac-5 yielded the dications rac-[M(diphos)(IsMePCH(2)PMeI(5))][OTf](2) (M(diphos) = Pd(dppe) (7), Pt(dppe) (9)) and a 1/1 mixture of the C-2-symmetric diastereomers [Pt((R,R)-Me-DuPhos)(IsMePCH(2)PMeIs)][OTf](2) (11a,b). Treatment of 2 and 3 with 2 equiv of methyl triflate gave the dications 6-9 as ca. 1/1 meso/rac mixtures, and methylation of 4 selectively gave one of the C-2-symmetric diastereomers, 11a. These alkylations proceeded via the observable monomethylated intermediates [M(diphos)(IsMePCH(2)PIs)][OTf] (12-14).

  DOI：

  10.1021/om3005367
• 作为产物：
  描述：

  2-溴-1,3,5-三异丙苯 在 lithium aluminium tetrahydride 、 magnesium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 21.0h， 生成 methylenebis(2,4,6-triisopropylphenylphosphine)
  参考文献：
  名称：

  Synthesis, Structure, Dynamics, and Selective Methylation of Platinum and Palladium Diphosphametallacyclobutane Complexes

  摘要：

  Treatment of M(dppe)Cl-2 (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)Cl-2 with IsHPCH(2)PHIs (1; Is = isityl = 2,4,6-(i-Pr)(3)C6H2) and 2 equiv of NaOSiMe3 gave the mononuclear diphosphametallacyclobutane complexes M(dppe)(IsPCH(2)PIs) (M = Pd (2), Pt (3)), or Pt((1,R)-Me-DuPhos)(IsPCH(2)PIs) (4). Dynamic processes involving phosphorus inversion and rotation about the P-C (1s) bonds in 2-4 were characterized by variable-temperature NMR spectroscopy, which suggested that each existed as a single C-2-symmetric diastereomer in solution, consistent with their solid-state structures determined by X-ray crystallography. The MiniPhos derivative IsMePCH(2)PMeIs (5) was prepared as a 5.5/1 rac/meso mixture by sequential arylation and methylation of Cl2PCH2PCl2. Alternatively, the catalyst precursor Pt((1,R)-Me-DuPhos)(Ph)(Cl) mediated alkylation of secondary phosphines in the presence of NaOSiMe3 to yield selectively meso-5 either from PHMe(1s) and CH2I2 or from 1 and MeI. Recrystallization and chromatography yielded diastereomerically enriched rac-5 and meso-5. Treatment of M(dppe)(OTf)(2) (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)(OTf)(2) with meso-5 gave the dications meso-[M(diphos)(IsMePCH(2)PMeIs)][OTf](2) (M(diphos) = Pd(dppe) (6), Pt(dppe) (8), Pt((R,R)-Me-DuPhos) (10)). Similar reactions of rac-5 yielded the dications rac-[M(diphos)(IsMePCH(2)PMeI(5))][OTf](2) (M(diphos) = Pd(dppe) (7), Pt(dppe) (9)) and a 1/1 mixture of the C-2-symmetric diastereomers [Pt((R,R)-Me-DuPhos)(IsMePCH(2)PMeIs)][OTf](2) (11a,b). Treatment of 2 and 3 with 2 equiv of methyl triflate gave the dications 6-9 as ca. 1/1 meso/rac mixtures, and methylation of 4 selectively gave one of the C-2-symmetric diastereomers, 11a. These alkylations proceeded via the observable monomethylated intermediates [M(diphos)(IsMePCH(2)PIs)][OTf] (12-14).

  DOI：

  10.1021/om3005367

文献信息

• Rhodium-Catalyzed Isomerization of a Bis(secondary phosphine) to an Unsymmetrical Diphosphine via P–C Cleavage and P–P and C–H Bond Formation
  作者：Perry M. Scheetz、David S. Glueck、Arnold L. Rheingold

  DOI：10.1021/acs.organomet.7b00515

  日期：2017.9.11

  To develop Rh-catalyzed dehydrocoupling for stereocontrolled synthesis of P–P bonds, we prepared potential intermediates, chiral rhodium phosphine-phosphido complexes, and investigated their stoichiometric and catalytic transformations. Treatment of [Rh(diphos*)(COD)][X] with the bis(secondary phosphine) IsHPCH2PHIs (1, Is = 2,4,6-(i-Pr)3C6H2) gave the cations [Rh(diphos*)(IsHPCH2PHIs)][X] (diphos*

  为了开发用于P-P键立体控制合成的Rh催化的脱氢偶联，我们制备了潜在的中间体，手性铑膦-膦基复合物，并研究了它们的化学计量和催化转化。用双（仲膦）IsHPCH 2 PHI （1，Is = 2,4,6-（i -Pr）3 C 6 H 2）处理[Rh（diphos *）（COD）] [X]得到阳离子[Rh（diphos *）（IsHPCH 2 PHIs ）] [X]（diphos * =（R，R）-Me-DuPhos（2），（R，R）-i -Pr-DuPhos（3）或（R，R）-Me-BPE（4）；X = BF 4或OTf）具有高非对映选择性，作为单个C 2对称非对映异构体。去质子化2 - 4用的NaN（森达3）2，得到膦膦螯合物的Rh（DIPHOS *）（IsHPCH 2 PIS）5 - 7具有高非对映选择性。在90°C下甲苯中5 – 7的热解引起异构化，得到非对映异构体混合物的Rh（diphos
• Effects of Linker Length on the Rate and Selectivity of Platinum-Catalyzed Asymmetric Alkylation of the Bis(isitylphosphino)alkanes IsHP(CH₂)_<i>n</i>PHIs (Is = 2,4,6-(<i>i</i>-Pr)₃C₆H₂, <i>n</i> = 1−5)
  作者：Timothy W. Chapp、Adam J. Schoenfeld、David S. Glueck

  DOI：10.1021/om100174c

  日期：2010.6.14

  Catalytic asymmetric alkylation of the bis(secondary phosphines) IsHP(CH2)(n)PHIs (1a-e, n = 1-5, Is = isityl = 2,4,6-(i-Pr)(3)C6H2) with benzyl bromide using the base NaOSiMe3 and the catalyst precursor Pt((R,R)-Me-DuPhos)(Ph)(Cl) gave the bis(tertiary phosphines) Is(PhCH2)P(CH2)(n)P(CH2Ph)Is (2a-e, n = 1-5) via the intermediates Is(PhCH2)P(CH2)(n)PHIs (4a-e, n = 1-5). The rates of these reactions depended strongly on n, in the order 1a < 1b < 1c approximate to 1d approximate to 1e. The bulkier bis(secondary phosphine) Mes*HP(CH2)(2)PHMe5* (5, Mes* = 2,4,6-(t-Bu)(3)C6H2) did not undergo catalytic alkylation under these conditions. The alkylation selectivity also depended on n. Alkylation of 1b was meso-selective, while alkylation of 1a,c-e was roe-selective, occurring with similar diastercoselectivity and enantioselectivity for the longer linkers (1c-e). The product ratios suggested that the catalyst controlled the selectivity for 1d,e, while substrate control operated for ethano-bridged 1b, with negative cooperativity. Substrate control also likely occurred for I a, for which competition from the background alkylation was significant. Analysis of the observed diastereo- and enantioselectivity for Pt-catalyzed alkylation of 1c and the mixed secondary/tertiary phosphine IsHP(CH2)(3)P(CH2Ph)Is (4c) yielded quantitative information on the selectivity of both P-C bond-forming steps, which was consistent with predominant catalyst control, altered slightly by the influence of the substrate.
• Bitterer, Frank; Brauer, David J.; Doerrenbach, Frank, Zeitschrift fur Naturforschung, B: Chemical Sciences, 1992, vol. 47, # 11, p. 1529 - 1540
  作者：Bitterer, Frank、Brauer, David J.、Doerrenbach, Frank、Fischer, Joerg、Stelzer, Othmar

  DOI：——

  日期：——
• Synthesis, Structure, Dynamics, and Selective Methylation of Platinum and Palladium Diphosphametallacyclobutane Complexes
  作者：Timothy W. Chapp、Adam J. Schoenfeld、Matthew D. Sanderson、Cory L. Chang、David S. Glueck、James A. Golen、Curtis E. Moore、Arnold L. Rheingold

  DOI：10.1021/om3005367

  日期：2012.8.13

  Treatment of M(dppe)Cl-2 (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)Cl-2 with IsHPCH(2)PHIs (1; Is = isityl = 2,4,6-(i-Pr)(3)C6H2) and 2 equiv of NaOSiMe3 gave the mononuclear diphosphametallacyclobutane complexes M(dppe)(IsPCH(2)PIs) (M = Pd (2), Pt (3)), or Pt((1,R)-Me-DuPhos)(IsPCH(2)PIs) (4). Dynamic processes involving phosphorus inversion and rotation about the P-C (1s) bonds in 2-4 were characterized by variable-temperature NMR spectroscopy, which suggested that each existed as a single C-2-symmetric diastereomer in solution, consistent with their solid-state structures determined by X-ray crystallography. The MiniPhos derivative IsMePCH(2)PMeIs (5) was prepared as a 5.5/1 rac/meso mixture by sequential arylation and methylation of Cl2PCH2PCl2. Alternatively, the catalyst precursor Pt((1,R)-Me-DuPhos)(Ph)(Cl) mediated alkylation of secondary phosphines in the presence of NaOSiMe3 to yield selectively meso-5 either from PHMe(1s) and CH2I2 or from 1 and MeI. Recrystallization and chromatography yielded diastereomerically enriched rac-5 and meso-5. Treatment of M(dppe)(OTf)(2) (M = Pd, Pt) or Pt((R,R)-Me-DuPhos)(OTf)(2) with meso-5 gave the dications meso-[M(diphos)(IsMePCH(2)PMeIs)][OTf](2) (M(diphos) = Pd(dppe) (6), Pt(dppe) (8), Pt((R,R)-Me-DuPhos) (10)). Similar reactions of rac-5 yielded the dications rac-[M(diphos)(IsMePCH(2)PMeI(5))][OTf](2) (M(diphos) = Pd(dppe) (7), Pt(dppe) (9)) and a 1/1 mixture of the C-2-symmetric diastereomers [Pt((R,R)-Me-DuPhos)(IsMePCH(2)PMeIs)][OTf](2) (11a,b). Treatment of 2 and 3 with 2 equiv of methyl triflate gave the dications 6-9 as ca. 1/1 meso/rac mixtures, and methylation of 4 selectively gave one of the C-2-symmetric diastereomers, 11a. These alkylations proceeded via the observable monomethylated intermediates [M(diphos)(IsMePCH(2)PIs)][OTf] (12-14).