IsHP(CH2)4PHIs | 1228778-65-1

• 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: IsHP(CH2)4PHIs
• 英文别名: [2,4,6-Tri(propan-2-yl)phenyl]-[4-[2,4,6-tri(propan-2-yl)phenyl]phosphanylbutyl]phosphane；[2,4,6-tri(propan-2-yl)phenyl]-[4-[2,4,6-tri(propan-2-yl)phenyl]phosphanylbutyl]phosphane
• CAS: 1228778-65-1
• 化学式: C₃₄H₅₆P₂
• 分子量: 526.766
• InChiKey: KHOHHJRXZYYLRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  36
• 可旋转键数：
  13
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 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：

  IsHP(CH2)4PHIs 、 溴甲苯 在 Pt((R,R)-Me-DuPhos)(Ph)(Cl) 、 sodium trimethylsilanolate 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 Is(PhCH2)P(CH2)4P(CH2Ph)Is 、 Is(PhCH2)P(CH2)4P(CH2Ph)Is 、 Is(PhCH2)P(CH2)4P(CH2Ph)Is
  参考文献：
  名称：

  Effects of Linker Length on the Rate and Selectivity of Platinum-Catalyzed Asymmetric Alkylation of the Bis(isitylphosphino)alkanes IsHP(CH₂)_nPHIs (Is = 2,4,6-(i-Pr)₃C₆H₂, n = 1−5)

  摘要：

  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.

  DOI：

  10.1021/om100174c
• 作为产物：
  描述：

  1,4-二溴丁烷 、 膦,[2,4,6-三(1-甲基乙基)苯基]- 在 potassium carbonate 、 potassium hydroxide 作用下， 以 二甲基亚砜 为溶剂， 反应 63.0h， 以383 mg的产率得到IsHP(CH2)4PHIs
  参考文献：
  名称：

  Effects of Linker Length on the Rate and Selectivity of Platinum-Catalyzed Asymmetric Alkylation of the Bis(isitylphosphino)alkanes IsHP(CH₂)_nPHIs (Is = 2,4,6-(i-Pr)₃C₆H₂, n = 1−5)

  摘要：

  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.

  DOI：

  10.1021/om100174c

文献信息

• 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.