methyl 2-[2-(diphenylphosphino)phenyl]acetate | 761402-24-8

• 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: methyl 2-[2-(diphenylphosphino)phenyl]acetate
• 英文别名: Methyl 2-(2-diphenylphosphanylphenyl)acetate
• CAS: 761402-24-8
• 化学式: C₂₁H₁₉O₂P
• 分子量: 334.354
• InChiKey: KIRMDOHRJFJXAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  24
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.1
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  methyl 2-[2-(diphenylphosphino)phenyl]acetate 在 sodium hydroxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 水 、 二甲基亚砜 为溶剂， 反应 3.0h， 生成 2-(2-(diphenylphosphino)phenyl)-3-methylbutanoic acid
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Decarboxylative [4+2] Dipolar Cycloaddition of 4-Vinyl-1,3-dioxan-2-ones with α,β-Disubstituted Nitroalkenes Enabled by a Benzylic Substituted P,N-Ligand

  摘要：

  The Pd-catalyzed asymmetric [4+2] cycloaddition reaction of an aliphatic 1,4-dipole with singly activated electron-deficient alkenes is realized for the first time, enabled by using a newly developed benzylic substituted P,N-ligand, affording tetrahydropyrans having three continuous chiral centers in high yields with high diastereo- and enantioselectivities. The rational transition states of the reaction as well as the role of the benzylic chiral center are proposed.

  DOI：

  10.1021/acs.orglett.0c01638
• 作为产物：
  描述：

  2-碘苯乙酸 在 4-二甲氨基吡啶 、 N,N-二异丙基乙胺 、 N,N'-二环己基碳二亚胺 、 1,4-双(二苯基膦)丁烷 、 palladium dichloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 40.0h， 生成 methyl 2-[2-(diphenylphosphino)phenyl]acetate
  参考文献：
  名称：

  Palladium-Catalyzed Asymmetric Decarboxylative [4+2] Dipolar Cycloaddition of 4-Vinyl-1,3-dioxan-2-ones with α,β-Disubstituted Nitroalkenes Enabled by a Benzylic Substituted P,N-Ligand

  摘要：

  The Pd-catalyzed asymmetric [4+2] cycloaddition reaction of an aliphatic 1,4-dipole with singly activated electron-deficient alkenes is realized for the first time, enabled by using a newly developed benzylic substituted P,N-ligand, affording tetrahydropyrans having three continuous chiral centers in high yields with high diastereo- and enantioselectivities. The rational transition states of the reaction as well as the role of the benzylic chiral center are proposed.

  DOI：

  10.1021/acs.orglett.0c01638

文献信息

• A Dramatic Switch of Enantioselectivity in Asymmetric Heck Reaction by Benzylic Substituents of Ligands
  作者：Wen-Qiong Wu、Qian Peng、Da-Xuan Dong、Xue-Long Hou、Yun-Dong Wu

  DOI：10.1021/ja7104174

  日期：2008.7.1

  synthesized. The Pd-complexes of these ligands show high catalytic activity and enantioselectivity in catalyzing the asymmetric Heck reaction. A dramatic switch in enantioselectivity is realized using ligands with and without substituents at the benzylic position of the ligand. Ligands 1 with H as the substituents offer products in (R)-configuration while ligands 2 with the methyl as substituents result

  已经合成了一系列苄基取代的 P、N-配体 1 和 2。这些配体的 Pd 配合物在催化不对称 Heck 反应中显示出高催化活性和对映选择性。使用在配体的苄基位置带有和不带有取代基的配体实现了对映选择性的显着转变。具有 H 作为取代基的配体 1 提供 (R)-构型的产物，而具有甲基作为取代基的配体 2 产生 (S)-构型的产物。在大多数情况下，实现了高对映选择性。反应机理的密度泛函理论计算以及 1a-PdCl 2 和 2a-PdCl 2 配合物的 X 射线分析为上述观察提供了合理的解释。
• Synthesis of new chiral benzylically substituted P,N-ligands and their applications in the asymmetric Heck reaction
  作者：Xue-Long Hou、Da Xuan Dong、Ke Yuan

  DOI：10.1016/j.tetasy.2004.05.030

  日期：2004.7

  A series of new chiral P,N-ligands with substituents at the benzylic position has been prepared. Their high catalytic activity is shown in the Pd-catalyzed asymmetric Heck reaction and allylic substitution reaction. (C) 2004 Elsevier Ltd. All rights reserved.