2-Tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole | 1268476-26-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-Tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole
• 英文别名: 2-tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole
• CAS: 1268476-26-1
• 化学式: C₁₄H₁₉N₂O₂P
• 分子量: 278.291
• InChiKey: CZHLRDYPSPDATB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  44.1
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-Tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole 在 palladium(II) bromide 作用下， 生成 trans-stilbene
  参考文献：
  名称：

  Imidazolio-substituted secondary phosphine oxides as potential carbene reagents

  摘要：

  New pre-ligands of 1-aryl-1H-imidazol-2-yl substituted secondary phosphine oxides (HRP(=O)-Im:SPO-Im) were prepared and characterized by spectroscopic means. The SPO-Im pre-ligands are able to tautomerize to their corresponding genuine ligands, the 1-aryl-1H-imidazol-2-yl substituted phosphinous acids ((HO)RP-Im:PA-Im) while the condition permitted. Further reactions of selected SPO-Im pre-ligands toward Pd(COD)Cl-2 or PdBr yielded bis-(PA-Im)-coordinated cis-palladium dichloride or dibromide complexes, respectively. These cis-palladium dihalide complexes are all having an intramolecular hydrogen bond between two coordinated PA-Im ligands (R(Im(H)(+))P-O-center dot center dot center dot HO-PRIm) by transferring a proton from one of the two P-OH groups to its free nitrogen site of imidazolyl substituents; and, therefore, imposes the formation of zwitterionic cis-form palladium complexes. Three crystal structures of these square-planar zwitterionic palladium complexes were determined by the X-ray diffraction methods. Additionally, two novel NHC carbene coordinated palladium complexes were obtained from the crystal-growing process of the above-mentioned zwitterionic cis-palladium dihalide complexes. The crystal structures of two NHC carbene coordinated palladium complexes were also successfully determined. Density-functional theory (DFT) calculations were carried out to substantiate the feasibility of the proposed reaction pathways for the formation of NHC carbene coordinated palladium complexes. Finally, applying selected SPO-Im pre-ligands to Heck reactions with pre-optimized reaction conditions exhibited satisfactory performances. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2015.08.041
• 作为产物：
  描述：

  2-溴苯甲醚 在 potassium phosphate 、 copper(l) iodide 、 正丁基锂 、 1,10-菲罗啉 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 50.0h， 生成 2-Tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole
  参考文献：
  名称：

  在温和条件下，钯 (II) 催化芳基卤化物和芳基硼​​酸与烯烃的 Heck 反应。

  摘要：

  在温和的反应条件下研究了一系列通用和选择性 Pd(II) 催化的 Heck 反应。第一个协议是采用基于咪唑的二级氧化膦 (SPO) 连接钯配合物 (6) 作为预催化剂开发的。芳基卤化物和烯烃的催化偶联导致以极好的产率形成相应的偶联产物。各种底物，包括富电子和缺电子烯烃，都能以高产率顺利转化为目标产物。与现有的在 Heck 反应中使用 SPO-Pd 配合物的方法相比，目前的策略具有反应条件温和和底物范围广的特点。此外，我们描述了芳基硼酸与烯烃的偶联，由 Pd(OAc)2 催化并在环境条件下使用 N-溴代琥珀酰亚胺作为添加剂。以中等至良好的产率获得了所得联芳基化合物。

  DOI：

  10.3762/bjoc.9.180
• 作为试剂：
  描述：

  对溴苯乙烯 、 苯硼酸 在 2-Tert-butylphosphonoyl-1-(2-methoxyphenyl)imidazole 、 palladium diacetate 、 potassium hydroxide 作用下， 以 四氢呋喃 为溶剂， 反应 10.0h， 以70%的产率得到4-乙烯基联苯
  参考文献：
  名称：

  新的布赫瓦尔德型次生氧化膦配体的制备及其在Suzuki-Miyaura反应中的应用

  摘要：

  两种对空气和水分稳定的仲氧化膦（SPO），即2-（叔丁基氢磷酰基）-1-（2-R-苯基）-1 H-咪唑（3a，R = H; 3b，R = OMe ）已准备好并进行了特征化。在仲氧化膦3a（或3b）与其对应的次膦酸3a'（或3b'）之间存在互变异构平衡。次膦酸3a'（或3b'）与Pd（COD）Cl 2（或PdBr 2）反应生成相应的单钯配合物双（2-（叔丁基氢磷酰基）-1-（2-R-苯基）-1 H咪唑）PDX 2（图5a，R = H，X =氯;图5b，R = OME，X =溴）在顺式-形式以及二钯配合物[（μ 2 -2-（叔-butylhydrophosphoryl）-1- （2-R-苯基）-1 H-咪唑-N，P）Pd（I）X] 2（6a，R ＝ H，X ＝ Cl；6b，R ＝ OMe，X ＝ Br）。次膦酸3a'和3b'在6a和6b的形成中充当P，N螯合配体，其特征在于直接的Pd（I）-P

  DOI：

  10.1021/om101132t

文献信息

• Imidazolio-substituted secondary phosphine oxides as potential carbene reagents
  作者：Yu-Chang Chang、Chih-Hung Chang、Lyu-Wei Wang、Ya-Han Liang、Dan-Fu Hu、Chia-Ming Weng、Kuo-Chung Mao、Fung-E Hong

  DOI：10.1016/j.poly.2015.08.041

  日期：2015.11

  New pre-ligands of 1-aryl-1H-imidazol-2-yl substituted secondary phosphine oxides (HRP(=O)-Im:SPO-Im) were prepared and characterized by spectroscopic means. The SPO-Im pre-ligands are able to tautomerize to their corresponding genuine ligands, the 1-aryl-1H-imidazol-2-yl substituted phosphinous acids ((HO)RP-Im:PA-Im) while the condition permitted. Further reactions of selected SPO-Im pre-ligands toward Pd(COD)Cl-2 or PdBr yielded bis-(PA-Im)-coordinated cis-palladium dichloride or dibromide complexes, respectively. These cis-palladium dihalide complexes are all having an intramolecular hydrogen bond between two coordinated PA-Im ligands (R(Im(H)(+))P-O-center dot center dot center dot HO-PRIm) by transferring a proton from one of the two P-OH groups to its free nitrogen site of imidazolyl substituents; and, therefore, imposes the formation of zwitterionic cis-form palladium complexes. Three crystal structures of these square-planar zwitterionic palladium complexes were determined by the X-ray diffraction methods. Additionally, two novel NHC carbene coordinated palladium complexes were obtained from the crystal-growing process of the above-mentioned zwitterionic cis-palladium dihalide complexes. The crystal structures of two NHC carbene coordinated palladium complexes were also successfully determined. Density-functional theory (DFT) calculations were carried out to substantiate the feasibility of the proposed reaction pathways for the formation of NHC carbene coordinated palladium complexes. Finally, applying selected SPO-Im pre-ligands to Heck reactions with pre-optimized reaction conditions exhibited satisfactory performances. (C) 2015 Elsevier Ltd. All rights reserved.
• Palladium(II)-catalyzed Heck reaction of aryl halides and arylboronic acids with olefins under mild conditions
  作者：Tanveer Mahamadali Shaikh、Fung-E Hong

  DOI：10.3762/bjoc.9.180

  日期：——

  A series of general and selective Pd(II)-catalyzed Heck reactions were investigated under mild reaction conditions. The first protocol has been developed employing an imidazole-based secondary phosphine oxide (SPO) ligated palladium complex (6) as a precatalyst. The catalytic coupling of aryl halides and olefins led to the formation of the corresponding coupled products in excellent yields. A variety

  在温和的反应条件下研究了一系列通用和选择性 Pd(II) 催化的 Heck 反应。第一个协议是采用基于咪唑的二级氧化膦 (SPO) 连接钯配合物 (6) 作为预催化剂开发的。芳基卤化物和烯烃的催化偶联导致以极好的产率形成相应的偶联产物。各种底物，包括富电子和缺电子烯烃，都能以高产率顺利转化为目标产物。与现有的在 Heck 反应中使用 SPO-Pd 配合物的方法相比，目前的策略具有反应条件温和和底物范围广的特点。此外，我们描述了芳基硼酸与烯烃的偶联，由 Pd(OAc)2 催化并在环境条件下使用 N-溴代琥珀酰亚胺作为添加剂。以中等至良好的产率获得了所得联芳基化合物。
• Preparation of New Buchwald-Type Secondary Phosphine Oxide Ligands and Applications in Suzuki−Miyaura Reactions
  作者：Dan-Fu Hu、Chia-Ming Weng、Fung-E Hong

  DOI：10.1021/om101132t

  日期：2011.3.14

  Two air- and moisture-stable secondary phosphine oxides (SPOs), namely, 2-(tert-butylhydrophosphoryl)-1-(2-R-phenyl)-1H-imidazole (3a, R = H; 3b, R = OMe) were prepared and characterized. A tautomeric equilibrium exists between the secondary phosphine oxide 3a (or 3b) and its corresponding phosphinous acid 3a′ (or 3b′). The reaction of phosphinous acid 3a′ (or 3b′) with Pd(COD)Cl2 (or PdBr2) yielded

  两种对空气和水分稳定的仲氧化膦（SPO），即2-（叔丁基氢磷酰基）-1-（2-R-苯基）-1 H-咪唑（3a，R = H; 3b，R = OMe ）已准备好并进行了特征化。在仲氧化膦3a（或3b）与其对应的次膦酸3a'（或3b'）之间存在互变异构平衡。次膦酸3a'（或3b'）与Pd（COD）Cl 2（或PdBr 2）反应生成相应的单钯配合物双（2-（叔丁基氢磷酰基）-1-（2-R-苯基）-1 H咪唑）PDX 2（图5a，R = H，X =氯;图5b，R = OME，X =溴）在顺式-形式以及二钯配合物[（μ 2 -2-（叔-butylhydrophosphoryl）-1- （2-R-苯基）-1 H-咪唑-N，P）Pd（I）X] 2（6a，R ＝ H，X ＝ Cl；6b，R ＝ OMe，X ＝ Br）。次膦酸3a'和3b'在6a和6b的形成中充当P，N螯合配体，其特征在于直接的Pd（I）-P