1-(di-tert-butylphosphino)heptan-1-one | 1334649-42-1

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机膦及其衍生物
• 英文名称: 1-(di-tert-butylphosphino)heptan-1-one
• 英文别名: 1-Ditert-butylphosphanylheptan-1-one；1-ditert-butylphosphanylheptan-1-one
• CAS: 1334649-42-1
• 化学式: C₁₅H₃₁OP
• 分子量: 258.384
• InChiKey: GIRLLLIBTRAWIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  bis[dichloro(pentamethylcyclopentadienyl)iridium(III)] 、 1-(di-tert-butylphosphino)heptan-1-one 以 四氢呋喃 为溶剂， 以85%的产率得到[Cp*Ir(^tBu₂P{heptanoyl})Cl₂]
  参考文献：
  名称：

  阴离子铱（III）配合物[Cp * Ir（OTf）3 ] [Ag { t Bu 2 P（庚酰基）}]的合成和反应活性

  摘要：

  描述了带有不寻常的二叔丁基庚酰基膦配体的铱配合物的合成。在探索该络合物的化学过程中，发现在三氟甲磺酸银存在下，酰基膦配体容易地被金属过渡成银。结果是形成新的阴离子铱络合物。X射线晶体结构显示阴离子[Cp * Ir（OTf）3 ] -充当银的螯合配体。还描述了这种复合物在小分子存在下的反应性。

  DOI：

  10.1021/om200639e
• 作为产物：
  描述：

  二-叔丁基膦 、 庚酰氯 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 1-(di-tert-butylphosphino)heptan-1-one
  参考文献：
  名称：

  Site-Selective Alkyl Dehydrogenation of a Coordinated Acylphosphine Ligand

  摘要：

  Regio- and stereoselective alkane dehydrogenation is a difficult challenge in organometallic chemistry. Intermolecular reactions of this type typically produce numerous olefin stereo- and regioisomers. Herein, we report our initial investigations into the intramolecular dehydrogenation of a datively bound alkyl ligand, demonstrating the first example of a site-selective dehydrogenation of an unactivated acyclic alkyl group. The alkyl group is located on an acylphosphine ligand that is coordinated to a Cp*IrCl2 monomer. A mechanistic proposal, guided by the isolation of a dimeric iridium complex and supported by computational results, is also described.

  DOI：

  10.1021/om300471h

文献信息

• Synthesis and Reactivity of the Anionic Iridium(III) Complex [Cp*Ir(OTf)₃][Ag{^<i>t</i>Bu₂P(heptanoyl)}]
  作者：Sean M. Whittemore、Judith Gallucci、James P. Stambuli

  DOI：10.1021/om200639e

  日期：2011.10.10

  The synthesis of an iridium complex bearing the unusual di-tert-butylheptanoylphosphine ligand is described. In exploring the chemistry of this complex, it was found that the acylphosphine ligand underwent facile transmetalation to silver in the presence of silver triflate. The result was the formation of a novel anionic iridium complex. The X-ray crystal structure revealed that the anion [Cp*Ir(OTf)3]−

  描述了带有不寻常的二叔丁基庚酰基膦配体的铱配合物的合成。在探索该络合物的化学过程中，发现在三氟甲磺酸银存在下，酰基膦配体容易地被金属过渡成银。结果是形成新的阴离子铱络合物。X射线晶体结构显示阴离子[Cp * Ir（OTf）3 ] -充当银的螯合配体。还描述了这种复合物在小分子存在下的反应性。
• Site-Selective Alkyl Dehydrogenation of a Coordinated Acylphosphine Ligand
  作者：Sean M. Whittemore、Ryan J. Yoder、James P. Stambuli

  DOI：10.1021/om300471h

  日期：2012.9.10

  Regio- and stereoselective alkane dehydrogenation is a difficult challenge in organometallic chemistry. Intermolecular reactions of this type typically produce numerous olefin stereo- and regioisomers. Herein, we report our initial investigations into the intramolecular dehydrogenation of a datively bound alkyl ligand, demonstrating the first example of a site-selective dehydrogenation of an unactivated acyclic alkyl group. The alkyl group is located on an acylphosphine ligand that is coordinated to a Cp*IrCl2 monomer. A mechanistic proposal, guided by the isolation of a dimeric iridium complex and supported by computational results, is also described.