4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole | 875439-13-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole
• 英文别名: (4-Tert-butyl-1-methylimidazol-2-yl)-di(propan-2-yl)phosphane
• CAS: 875439-13-7
• 化学式: C₁₄H₂₇N₂P
• 分子量: 254.356
• InChiKey: XKQQVSHREHFHCJ-UHFFFAOYSA-N

物化性质

• 沸点：
  329.3±35.0 °C(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  17.8
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole 以 苯 为溶剂， 生成 trans-bis(di-isopropyl-(1-methyl-4-tert-butylimidazol-2-yl)phosphine)Pd(methyl)(triflate)
  参考文献：
  名称：

  Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine Ligands on Pd(0) and Pd(II)

  摘要：

  Low-coordinate organometallic complexes are important in structure and catalysis, and hemilability or secondary interactions such as hydrogen bonding enabled by hybrid ligands are receiving increasing attention. To study the factors controlling these phenomena, three new imidazol-2-ylphosphine ligands, L, were made. In these ligands, the bulk around P and the hindrance at the basic and potentially coordinating imidazole N-3 were varied. Remarkably, L2Pd(0) complexes 3a-c were shown to be two-coordinate, 12-electron species, despite the availability of imidazole N-3 to enter into eta(2)-P,N chelation. In oxidative additions of C-X bonds to the Pd(0) complexes, reaction rates and products could be controlled by the nature of the C and X groups and the R groups on the phosphine. Most significantly, whereas 4c-Phl and 4c-MeOTf from 3c are normal trans-bis(phosphine)Pd(R)(X) species, 5a-Phl, 5a-PhBr, and 5b-Phl from 3a and 3b were shown by X-ray diffraction to be a monomeric species with a single eta(2)-P,N-chelating phosphine. From 3a and methyl triflate, an ionic complex [6a-Me](+)[OTf](-) with one chelating and one nonchelating phosphine was formed, with temperature-dependent windshield-wiper exchange of the two, showing hemilability. Thus, large phosphine substituents (R = tert-butyl rather than isopropyl) favor chelation. The chelate Pd-imidazole N-3 bond is longer when the heterocyclic nitrogen is hindered by an adjacent tert-butyl group at C-4 (comparing 5a-Phl and 5b-Phl). Finally, whereas in [8b-Ph](+)[OTf](-) from 5b-Phl and isopropylamine, the amine coordinates without chelate opening or hydrogen bonding, in [10c-Me](+)[OTf](-) made from 4c-MeOTf and isopropylamine, the amine is not only coordinated at N but also donates a hydrogen bond to each phosphine imidazol-2-yl substituent.

  DOI：

  10.1021/ja054779u
• 作为产物：
  描述：

  氯二异丙基膦 、 4-叔丁基-1-甲基-1H-咪唑 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 1.0h， 以73%的产率得到4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole
  参考文献：
  名称：

  Changes in Coordination of Sterically Demanding Hybrid Imidazolylphosphine Ligands on Pd(0) and Pd(II)

  摘要：

  Low-coordinate organometallic complexes are important in structure and catalysis, and hemilability or secondary interactions such as hydrogen bonding enabled by hybrid ligands are receiving increasing attention. To study the factors controlling these phenomena, three new imidazol-2-ylphosphine ligands, L, were made. In these ligands, the bulk around P and the hindrance at the basic and potentially coordinating imidazole N-3 were varied. Remarkably, L2Pd(0) complexes 3a-c were shown to be two-coordinate, 12-electron species, despite the availability of imidazole N-3 to enter into eta(2)-P,N chelation. In oxidative additions of C-X bonds to the Pd(0) complexes, reaction rates and products could be controlled by the nature of the C and X groups and the R groups on the phosphine. Most significantly, whereas 4c-Phl and 4c-MeOTf from 3c are normal trans-bis(phosphine)Pd(R)(X) species, 5a-Phl, 5a-PhBr, and 5b-Phl from 3a and 3b were shown by X-ray diffraction to be a monomeric species with a single eta(2)-P,N-chelating phosphine. From 3a and methyl triflate, an ionic complex [6a-Me](+)[OTf](-) with one chelating and one nonchelating phosphine was formed, with temperature-dependent windshield-wiper exchange of the two, showing hemilability. Thus, large phosphine substituents (R = tert-butyl rather than isopropyl) favor chelation. The chelate Pd-imidazole N-3 bond is longer when the heterocyclic nitrogen is hindered by an adjacent tert-butyl group at C-4 (comparing 5a-Phl and 5b-Phl). Finally, whereas in [8b-Ph](+)[OTf](-) from 5b-Phl and isopropylamine, the amine coordinates without chelate opening or hydrogen bonding, in [10c-Me](+)[OTf](-) made from 4c-MeOTf and isopropylamine, the amine is not only coordinated at N but also donates a hydrogen bond to each phosphine imidazol-2-yl substituent.

  DOI：

  10.1021/ja054779u
• 作为试剂：
  描述：

  tert-butyl(pent-4-en-1-yloxy)diphenylsilane 在 4-(tert-butyl)-2-(diisopropylphosphino)-1-methyl-1H-imidazole 、 C₂₆H₄₅N₃PRu⁽¹⁺⁾*F₆P^(1-) 、 C₂₈H₄₉N₄PRu⁽¹⁺⁾*F₆P^(1-) 作用下， 以 氘代丙酮 为溶剂， 反应 48.0h， 以90.3%的产率得到(E)-tert-butyl (pent-3-enyloxy)diphenylsilane
  参考文献：
  名称：

  Terminal alkene monoisomerization catalysts and methods

  摘要：

  该发明提供了新型催化剂和使用催化剂的方法，用于控制双键的位置以及顺式/反式选择性，在将末端烯烃异构化为它们的2-异构体过程中。这些催化剂，比如（五甲基环戊二烯基）钌配方1和3，具有双功能膦基，可用于这些方法。配方1+3的1摩尔%的催化剂负载可用于在40-70°C下生产（E）-2-烯烃；较高的催化剂负载可以使用更低的温度。无乙腈催化剂可以在较低的负载、室温和不到一天的时间内完成与配方1+3相同的结果。这种新型催化系统最小化了烯烃异构体的热力学平衡，因此可以生成非官能化和官能化烯烃的反式-2-烯烃。

  公开号：

  US09708236B2

文献信息

• Terminal alkene monoisomerization catalysts and methods
  申请人：San Diego State University Research Foundation

  公开号：US09708236B2

  公开（公告）日：2017-07-18

  The invention provides novel catalysts and methods of using catalysts for controlling the position of a double bond and cis/trans-selectivity in isomerization of terminal alkenes to their 2-isomers. Catalysts such as (pentamethylcyclopentadienyl)Ru formulas 1 and 3 having a bifunctional phosphine can be used in the methods. A catalyst loading of 1 mol % of formulas 1+3 can be employed for the production of (E)-2-alkenes at 40-70° C.; lower temperatures can be used with higher catalyst loading. Acetonitrile-free catalysts can be used at lower loadings, room temperature, and in less than a day to accomplish the same results as catalysts 1+3. The novel catalyst systems minimize thermodynamic equilibration of alkene isomers, so that the trans-2-alkenes of both non-functionalized and functionalized alkenes can be generated.

  该发明提供了新型催化剂和使用催化剂的方法，用于控制双键的位置以及顺式/反式选择性，在将末端烯烃异构化为它们的2-异构体过程中。这些催化剂，比如（五甲基环戊二烯基）钌配方1和3，具有双功能膦基，可用于这些方法。配方1+3的1摩尔%的催化剂负载可用于在40-70°C下生产（E）-2-烯烃；较高的催化剂负载可以使用更低的温度。无乙腈催化剂可以在较低的负载、室温和不到一天的时间内完成与配方1+3相同的结果。这种新型催化系统最小化了烯烃异构体的热力学平衡，因此可以生成非官能化和官能化烯烃的反式-2-烯烃。
• Dynamic π-Bonding of Imidazolyl Substituent in a Formally 16-Electron Cp*Ru(κ²-<i>P</i>,<i>N</i>)⁺ Catalyst Allows Dramatic Rate Increases in (<i>E</i>)-Selective Monoisomerization of Alkenes
  作者：Erik R. Paulson、Curtis E. Moore、Arnold L. Rheingold、David P. Pullman、Ryan W. Sindewald、Andrew L. Cooksy、Douglas B. Grotjahn

  DOI：10.1021/acscatal.8b04345

  日期：2019.8.2

  in κ2-P,N coordination. For the first time, we show direct experimental evidence that the PN ligand has accepted a proton from the substrate by characterizing the intermediate Cp*Ru[η3-allyl][κ1-P)P–N+H], which highlights the essential role of the bifunctional ligand in promoting rapid and selective alkene isomerizations. Moreover, kinetic studies and computations reveal the role of alkene binding in

  烯烃异构化可以是一种原子经济的方法，可用于生成范围广泛的用于合成的烯烃中间体，但是完全平衡的二取代内部烯烃的混合物通常包含大量的位置异构体和几何异构体（E和Z）。用于烯烃异构化的大多数经典催化剂体系都难以动力学控制位置异构或E / Z异构。我们报告了配位不饱和，形式为16电子的Cp * Ru催化剂5，它可促进线性1-烯烃同时向其内部类似物进行区域和立体选择性异构化，从而提供（E）-2-烯烃大于95％。由于无腈催化剂5比以前发表的含腈类似物2 + 2a快400倍以上，因此在15分钟至4小时内完成5个完全环境温度反应的0.1-0.5摩尔％非常合理的负载量。的UV-vis，NMR，和计算研究描绘κ上膦作为hemilabile，四-电子给体的咪唑基片段2 - P，Ñ协调。对于第一次，我们显示直接的实验证据表明，PN配体已经通过表征中间的Cp *茹[η接受从基板的质子3 -烯丙基] [κ 1 - P）PN+
• BIFUNCTIONAL CATALYSTS FOR EXTENSIVE ISOMERIZATION OF UNSATURATED HYDROCARBONS
  申请人：Grotjahn Douglas

  公开号：US20090143585A1

  公开（公告）日：2009-06-04

  The current invention provides novel bifunctional catalysts. The bifunctional catalysts are prepared from phosphine ligands and a cyclopentadienyl metal complex and are useful for forming isomers of hydrocarbon species. The hydrocarbon can be an alkenol having the alkene and alcohol groups far apart and the catalyst will move the double bond across numerous carbon atoms. The hydrocarbon can also be an achiral alkenol and the catalyst will form a chiral alcohol therefrom. Moreover, deuterated water may be added to the isomerization reaction mixture for forming deuterated hydrocarbon species.

  本发明提供了新型的双功能催化剂。这些双功能催化剂由膦配体和环戊二烯基金属配合物制备而成，可用于形成烃种类的异构体。烃可以是烯醇，其烯烃和羟基远离，催化剂将使双键移动到许多碳原子上。烃也可以是非手性烯醇，催化剂将形成手性醇。此外，可以向异构化反应混合物中添加氘化水以形成氘代烃种类。
• Experimental and Computational Study of the Transformation of Terminal Alkynes to Vinylidene Ligands on <i>trans</i>-(Chloro)bis(phosphine)Rh Fragments and Effects of Phosphine Substituents
  作者：Douglas B. Grotjahn、Xi Zeng、Andrew L. Cooksy、W. Scott Kassel、Antonio G. DiPasquale、Lev. N. Zakharov、Arnold L. Rheingold

  DOI：10.1021/om700355r

  日期：2007.7.1

  the two-dimensional reaction surface, combined density functional/molecular mechanics calculations predict that η2-(C,H) alkyne complex 3 is in a fast equilibrium with the lower energy hydrido(alkynyl) complex 4, and neither species is expected to be present at observable concentrations. Eyring model estimates of the rate constants from these computational data predict the available experimental values

  实验和计算证据表明标题Rh（I）金属片段上末端炔的单分子转化。在双交叉实验中缺乏同位素加扰与先前提出的双分子途径不一致。着眼于单分子流形，炔与金属的结合形成Rh（I）炔π-络合物2，其异构化为Rh（III）氢化（炔基）物种4，最终导致Rh（I）亚乙烯基产物5。在制备不含炔烃的前体时，使用杂环配体（i -Pr）2 PIm'（1b，Im'= 1-甲基-4-叔丁基咪唑-2-基）导致形成物种8具有不稳定的P，N螯合物，而几何上相似的邻甲苯基配体在甲基处发生金属化，因此不适合进行炔烃转化研究。比较动力学研究1B和（我-Pr）2 PPH（1C）所允许的炔结合事件和的转换确定速率常数的2至5（后者，ķ 2 - 5，速度更快9.6倍为1B）。基于二维反应表面的扫描，组合密度泛函/分子力学计算预测，η 2 - （C，H）炔复杂3与较低能量的氢化（炔基）配合物4处于快速平衡状态，并且预计没有两种物质以可观察到
• TERMINAL ALKENE MONOISOMERIZATION CATALYSTS AND METHODS
  申请人：San Diego State University Research Foundation

  公开号：US20150231621A1

  公开（公告）日：2015-08-20

  The invention provides novel catalysts and methods of using catalysts for controlling the position of a double bond and cis/trans-selectivity in isomerization of terminal alkenes to their 2-isomers. Catalysts such as (pentamethylcyclopentadienyl)Ru formulas 1 and 3 having a bifunctional phosphine can be used in the methods. A catalyst loading of 1 mol % of formulas 1+3 can be employed for the production of (E)-2-alkenes at 40-70° C.; lower temperatures can be used with higher catalyst loading. Acetonitrile-free catalysts can be used at lower loadings, room temperature, and in less than a day to accomplish the same results as catalysts 1+3. The novel catalyst systems minimize thermodynamic equilibration of alkene isomers, so that the trans-2-alkenes of both non-functionalized and functionalized alkenes can be generated.

  本发明提供了一种新型催化剂及其使用方法，用于控制末端烯烃的异构化反应中双键位置和顺反式选择性的产生。可以使用具有双功能膦基的催化剂，例如（五甲基环戊二烯基）Ru公式1和3。在40-70°C下，可以使用1＋3公式的1摩尔％的催化剂负载来生产（E）-2-烯烃；使用更高的催化剂负载可以使用更低的温度。无乙腈催化剂可以在较低的负载、室温下使用，并在不到一天的时间内完成与1+3催化剂相同的结果。新型催化剂系统最小化烯烃异构体的热力学平衡，从而可以产生非功能化和功能化烯烃的反式-2-烯烃。