(diphenylphosphino)-3-tert-butylcyclopentadienyllithium

• 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: (diphenylphosphino)-3-tert-butylcyclopentadienyllithium
• 英文别名: 1-diphenylphosphino-3-tert-butylcyclopentadienyllithium；1-diphenylphoshino-3-tert-butylcyclopentadienyllitium；diphenylphosphino-3-tert-butylcyclopentadienyllithium；Lithium;(3-tert-butylcyclopenta-2,4-dien-1-yl)-diphenylphosphane；lithium;(3-tert-butylcyclopenta-2,4-dien-1-yl)-diphenylphosphane
• 化学式: C₂₁H₂₂P*Li
• 分子量: 312.32
• InChiKey: VQCOSJSIOYIYQQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.47
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (methoxymethylidene)dimethylammonium methyl sulfate 、 (diphenylphosphino)-3-tert-butylcyclopentadienyllithium 以 四氢呋喃 为溶剂， 以86%的产率得到N-{[4-tert-butyl-2-(diphenylphosphino)cyclopenta-2,4-dien-1-ylidene]methyl}-N,N-dimethylamine
  参考文献：
  名称：

  Converging and Diverging Synthetic Strategies to Tetradentate (N,N′)-Diaminomethyl,(P,P′)-Ferrocenyl Ligands: Influence of tert-Butyl Groups on Ferrocene Backbone Conformation

  摘要：

  Hexasubstituted hybrid tetradentate (N,N',P,P')-ferrocenes bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies: a "diverging" synthesis involving successive functionalization of preformed di-tert-butylated ferrocene and a "converging" assembly of the species from appropriately substituted cyclopentadienyl rings. While the new cydopentadienyl salts formed are of interest, their assembly with iron dichloride used as a "converging" way to produce tetradentate ferrocene ligands presented several drawbacks. Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene derivatives was found convenient to further form (N,N'-aminomethyl,(P,P'-tert-butylated-ferrocenyl diphosphines by N-directed ortho-metalation. The novel N-2-didentate and N2P2-tetradentate tert-butylated ferrocene compounds were all synthesized in good to high yields (48-96%) and tolerated aryl, alkyl, and heteroaryl phosphino groups as substituents on nitrogen and phosphorus atoms. They were characterized by X-ray diffraction and multinuclear NMR (H-1, C-13, P-31, N-15). We observed the conformation control provided to rac-(N,N'-diaminomethyl-(P,P'-tert-butylated-ferrocenyldiphosphines with in particular the systematic near-eclipsed conformation of aminomethyl groups. This conformation is at the origin of the unexpected formation at RT of a zwitterionic cyclopalladate from an (aminomethyl)ferrocene derivative, arising from intramolecular Cp-proton transfer to the proximate free amino group by simple C-H activation reaction in the presence of palladium dichloride.

  DOI：

  10.1021/acs.organomet.5b00601
• 作为产物：
  描述：

  叔丁基环戊二烯并二烯锂 、 二苯基氯化膦 在 正丁基锂 作用下， 以 甲苯 、 乙醚 为溶剂， 反应 14.0h， 以87%的产率得到(diphenylphosphino)-3-tert-butylcyclopentadienyllithium
  参考文献：
  名称：

  新的1,1'-或1,2-或1,3-双（二苯基膦基）二茂铁

  摘要：

  使用FeCl 2和适当取代的环戊二烯基盐LiC 5 H 3 -1,3-（PPh 2）2，LiC 5 H 3 -1-PPh 2 -3-之间的反应报道了具有大取代基的二茂铁基膦的合成。t Bu，LiC 5 H 2 -1,2-（PPh 2）2 -4- t Bu。这种策略导致生成双膦，三膦和四膦，而其他用于制备取代二茂铁的通道则无法获得双膦，三膦和四膦。[C 5 H 3 -1.3-（PPh 2）2]（C 5 H 5）Fe，[C 5 H 3 -1-PPh 2 -3- t Bu] 2 Fe外消旋和内消旋和[C 5 H 2 -1,2-（PPh 2）2 -4- t通过单晶X射线衍射研究表征了Bu]（C 5 H 5）Fe。

  DOI：

  10.1016/s0022-328x(99)00736-6

文献信息

• Conformational Control of Metallocene Backbone by Cyclopentadienyl Ring Substitution: A New Concept in Polyphosphane Ligands Evidenced by “Through-Space” Nuclear Spin−Spin Coupling. Application in Heteroaromatics Arylation by Direct C−H Activation
  作者：Radomyr V. Smaliy、Matthieu Beaupérin、Hélène Cattey、Philippe Meunier、Jean-Cyrille Hierso、Julien Roger、Henri Doucet、Yannick Coppel

  DOI：10.1021/om8012162

  日期：2009.6.8

  conformation of the ferrocene backbone in solution. The palladium complexes of the triphosphane ligand 6 and the diphosphane 1,1′-bis(diphenylphosphino)-3,3′-di(triphenyl)methylferrocene (7) were successfully used in the direct C−H activation of electron-rich heteroaromatics for coupling to demanding aryl bromides, whether electron rich and/or sterically congested. Products such as 2-butyl-5-(4-methoxyphenyl)furan

  本研究涉及二茂铁基聚膦配体中茂金属主链的构象控制及其在高局部钯催化的直接CH活化下的杂芳基芳基化反应中的性能。合成了新的取代的环戊二烯基环，该环允许组装原始的三和二膦烷。庞大的环戊二烯基锂盐二苯基膦基-3-（三苯基）甲基环戊二烯基锂（4）和1,2-双（二苯基膦基）-4-（三苯基）甲基环戊二烯基锂（5））以极高的收率制备。进行这些新的受阻环戊二烯基盐（Cp）与其他Cp片段的组装，以制备具有受控构象的二茂铁基配体。1,1-构象的比较'，2-三（二苯基膦基）-3'，4 -二-叔-butylferrocene（3）和1,1'，2-三（二苯基膦基）-3' - （三苯基）甲基-4-叔丁基二茂铁（6）使我们能够首次确定在没有ansa桥的情况下有效控制二茂铁骨架上膦基取代基的取向的条件。通过溶液中的多核NMR和固态X射线衍射对这些金属配体进行表征，重点研究了未键合的J PP自旋-自旋耦合。这些异常的偶联对
• Copper(I) Iodide Polyphosphine Adducts at Low Loading for Sonogashira Alkynylation of Demanding Halide Substrates: Ligand Exchange Study between Copper and Palladium
  作者：Matthieu Beaupérin、Andre Job、Hélène Cattey、Sylviane Royer、Philippe Meunier、Jean-Cyrille Hierso

  DOI：10.1021/om1003336

  日期：2010.6.28

  prestabilization of copper iodide with a multidentate ferrocenyl phosphine ligand promotes the palladium-catalyzed cross-coupling of demanding halides with phenylacetylene in a selective way. Novel CuI-triphosphine adducts are described in the solid state and in solution. Their use allowed the introduction of the copper iodide cocatalyst in unprecedented low amounts (0.4 to 0.1 mol %) in systems also employing

  带有多齿二茂铁基膦配体的碘化铜的预稳定作用促进了选择性卤化物与苯基乙炔的钯催化交叉偶联。以固态和溶液形式描述了新型的CuI-三膦加合物。它们的使用允许在系统也采用低量的“配体-自由” [Pd的前所未有的低的量引入碘化铜助催化剂的（0.4〜0.1摩尔％）II（η 3 -烯丙基）CL] 2前体（0.2至0.05mol％）。报道了底物的范围，并且有效地偶联了电子或空间失活的溴化物。关于芳基氯化物，还使用这种创新的低金属含量催化系统偶联了贫电子活化的底物。本文讨论了一些很少涉及的机械方面。特别地，发现通过NMR监测的配体从铜到钯的转移是不同的，这取决于多膦配体。与使用5 mol％的CuI与钯相反，抑制二炔的形成也是一个令人感兴趣的特征，其是由少量的预稳定铜物种提供的。值得注意的是，由1,2-双（二苯基膦基）-1'-（二异丙基膦基）-4-叔丁基形成的碘化亚铜（I）膦加合物6-丁基二茂铁，也仅在铜条件
• Converging and Diverging Synthetic Strategies to Tetradentate (<i>N</i>,<i>N</i>′)-Diaminomethyl,(<i>P</i>,<i>P</i>′)-Ferrocenyl Ligands: Influence of <i>tert</i>-Butyl Groups on Ferrocene Backbone Conformation
  作者：Fatima Allouch、Nejib Dwadnia、Nikolay V. Vologdin、Yurii V. Svyaschenko、Hélène Cattey、Marie-José Penouilh、Julien Roger、Daoud Naoufal、Ridha Ben Salem、Nadine Pirio、Jean-Cyrille Hierso

  DOI：10.1021/acs.organomet.5b00601

  日期：2015.10.26

  Hexasubstituted hybrid tetradentate (N,N',P,P')-ferrocenes bearing phosphino and aminomethyl groups, plus hindering tert-butyl moieties, were synthesized by using two different strategies: a "diverging" synthesis involving successive functionalization of preformed di-tert-butylated ferrocene and a "converging" assembly of the species from appropriately substituted cyclopentadienyl rings. While the new cydopentadienyl salts formed are of interest, their assembly with iron dichloride used as a "converging" way to produce tetradentate ferrocene ligands presented several drawbacks. Conversely, the synthesis of new tert-butylated (aminomethyl)ferrocene derivatives was found convenient to further form (N,N'-aminomethyl,(P,P'-tert-butylated-ferrocenyl diphosphines by N-directed ortho-metalation. The novel N-2-didentate and N2P2-tetradentate tert-butylated ferrocene compounds were all synthesized in good to high yields (48-96%) and tolerated aryl, alkyl, and heteroaryl phosphino groups as substituents on nitrogen and phosphorus atoms. They were characterized by X-ray diffraction and multinuclear NMR (H-1, C-13, P-31, N-15). We observed the conformation control provided to rac-(N,N'-diaminomethyl-(P,P'-tert-butylated-ferrocenyldiphosphines with in particular the systematic near-eclipsed conformation of aminomethyl groups. This conformation is at the origin of the unexpected formation at RT of a zwitterionic cyclopalladate from an (aminomethyl)ferrocene derivative, arising from intramolecular Cp-proton transfer to the proximate free amino group by simple C-H activation reaction in the presence of palladium dichloride.
• New 1,1′- or 1,2- or 1,3-bis(diphenylphosphino)ferrocenes
  作者：Roland Broussier、Emmanuelle Bentabet、Patrick Mellet、Olivier Blacque、Patricia Boyer、Marek M. Kubicki、Bernard Gautheron

  DOI：10.1016/s0022-328x(99)00736-6

  日期：2000.4

  The syntheses of ferrocenyl phosphines with bulky substituents are reported using the reaction between FeCl2 and the suitably substituted cyclopentadienyl salts, LiC5H3-1,3-(PPh2)2, LiC5H3-1-PPh2-3-tBu, LiC5H2-1,2-(PPh2)2-4-tBu. This strategy leads to bi-, tri- and tetraphosphines, which cannot be obtained by the other access paths used to prepare substituted ferrocenes. [C5H3-1,3-(PPh2)2](C5H5)Fe

  使用FeCl 2和适当取代的环戊二烯基盐LiC 5 H 3 -1,3-（PPh 2）2，LiC 5 H 3 -1-PPh 2 -3-之间的反应报道了具有大取代基的二茂铁基膦的合成。t Bu，LiC 5 H 2 -1,2-（PPh 2）2 -4- t Bu。这种策略导致生成双膦，三膦和四膦，而其他用于制备取代二茂铁的通道则无法获得双膦，三膦和四膦。[C 5 H 3 -1.3-（PPh 2）2]（C 5 H 5）Fe，[C 5 H 3 -1-PPh 2 -3- t Bu] 2 Fe外消旋和内消旋和[C 5 H 2 -1,2-（PPh 2）2 -4- t通过单晶X射线衍射研究表征了Bu]（C 5 H 5）Fe。