2-tert-butoxy-6-diphenylphosphanyl-pyridine | 547740-44-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-tert-butoxy-6-diphenylphosphanyl-pyridine
• 英文别名: [6-[(2-Methylpropan-2-yl)oxy]pyridin-2-yl]-diphenylphosphane
• CAS: 547740-44-3
• 化学式: C₂₁H₂₂NOP
• 分子量: 335.386
• InChiKey: MCDYJORQMVOPLW-UHFFFAOYSA-N

物化性质

• 熔点：
  77 °C
• 沸点：
  432.1±30.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  24
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  22.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-tert-butoxy-6-diphenylphosphanyl-pyridine 在 甲酸 作用下， 反应 0.5h， 以92.5%的产率得到6-Dppon
  参考文献：
  名称：

  氢键作为均相催化中双齿供体配体的构建元素：末端烯烃的区域选择性加氢甲酰化

  摘要：

  描述了构建用于均相金属配合物催化的双齿配体的新概念。该概念依赖于单齿配体通过氢键的自组装。作为此类系统的原型，6-二苯基膦酰基-2-吡啶酮 (6-DPPon) 显示通过不寻常的吡啶酮/羟基吡啶氢键 (X 射线) 在过渡金属中心的配位球中形成螯合物。正如末端烯烃的高度区域选择性加氢甲酰化所证明的那样，这种氢键在催化反应中保持完整。观察到的区域选择性和反应性将 6-DPPon/铑体系列为末端烯烃 n-选择性加氢甲酰化最活跃和区域选择性的催化剂。

  DOI：

  10.1021/ja0348997
• 作为产物：
  描述：

  2,6-二氯吡啶 在 氨 、 sodium 作用下， 以 甲苯 为溶剂， 反应 8.0h， 生成 2-tert-butoxy-6-diphenylphosphanyl-pyridine
  参考文献：
  名称：

  氢键作为均相催化中双齿供体配体的构建元素：末端烯烃的区域选择性加氢甲酰化

  摘要：

  描述了构建用于均相金属配合物催化的双齿配体的新概念。该概念依赖于单齿配体通过氢键的自组装。作为此类系统的原型，6-二苯基膦酰基-2-吡啶酮 (6-DPPon) 显示通过不寻常的吡啶酮/羟基吡啶氢键 (X 射线) 在过渡金属中心的配位球中形成螯合物。正如末端烯烃的高度区域选择性加氢甲酰化所证明的那样，这种氢键在催化反应中保持完整。观察到的区域选择性和反应性将 6-DPPon/铑体系列为末端烯烃 n-选择性加氢甲酰化最活跃和区域选择性的催化剂。

  DOI：

  10.1021/ja0348997

文献信息

• Hydrogen Bonding as a Construction Element for Bidentate Donor Ligands in Homogeneous Catalysis:  Regioselective Hydroformylation of Terminal Alkenes
  作者：Bernhard Breit、Wolfgang Seiche

  DOI：10.1021/ja0348997

  日期：2003.6.1

  bidentate ligands for homogeneous metal complex catalysis is described. The concept relies on the self-assembly of monodentate ligands through hydrogen bonding. As a prototype of such systems, 6-diphenylphosphanyl-2-pyridone (6-DPPon) was shown to form a chelate in the coordination sphere of a transition metal center through unusual pyridone/hydroxypyridine hydrogen bonding (X-ray). This hydrogen bonding

  描述了构建用于均相金属配合物催化的双齿配体的新概念。该概念依赖于单齿配体通过氢键的自组装。作为此类系统的原型，6-二苯基膦酰基-2-吡啶酮 (6-DPPon) 显示通过不寻常的吡啶酮/羟基吡啶氢键 (X 射线) 在过渡金属中心的配位球中形成螯合物。正如末端烯烃的高度区域选择性加氢甲酰化所证明的那样，这种氢键在催化反应中保持完整。观察到的区域选择性和反应性将 6-DPPon/铑体系列为末端烯烃 n-选择性加氢甲酰化最活跃和区域选择性的催化剂。
• Ligand Self-Assembling through Complementary Hydrogen-Bonding in the Coordination Sphere of a Transition Metal Center: The 6-Diphenylphosphanylpyridin-2(1<i>H</i>)-one System
  作者：Urs Gellrich、Jing Huang、Wolfgang Seiche、Manfred Keller、Markus Meuwly、Bernhard Breit

  DOI：10.1021/ja108639e

  日期：2011.2.2

  Motivated by previous findings which had shown that transition metal catalysts based on the 6-diphenylphosphanylpyridone ligand (6-DPPon, 2) display properties as a self-assembling bidentate ligand metal complex, we have performed a thorough study on the bonding situation of this ligand, alone and in the coordination sphere of a late transition metal. Thus, combining a number of spectroscopic methods (UV-vis, IR, NMR, X-ray), we gained insights into the unique structural characteristics of 2. These experimental studies were corroborated by DFT calculations, which were in all cases in good agreement with the experimental results. The free ligand 2 prefers to exist as the pyridone tautomer 2A and dimerizes to the pyridone pyridone dimer 4A in solution as well as in the crystal state. The corresponding hydroxypyridine tautomer 2B is energetically slightly disfavored (ca. 0.9 kcal/mol within the up-conformer relevant for metal coordination); hence, hydrogen bond formation within the complex may easily compensate this small energy penalty. Coordination properties of 2 were studied in the coordination sphere of a platinum(II) center. As a model complex, [Cl2Pt(6-DPPon)(2)] (11) was prepared and investigated. All experimental and theoretical methods used prove the existence of a hydrogen-bonding interligand network in solution as well as in the crystal state of 11 between one 6-DPPon ligand existing as the pyridone tautomer 2A and the other ligand occupying the complementary hydroxypyridine form 2B. Dynamic proton NMR allowed to determine the barrier for interligand hydrogen bond breaking and, in combination with theory, enabled us to determine the enthalpic stabilization through hydrogen-bonding to contribute 14-15 kcal/mol.