4-allyl-2-methyl-4-phenylpyrrolidine | 1016983-72-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 4-allyl-2-methyl-4-phenylpyrrolidine
• 英文别名: 2-Methyl-4-phenyl-4-prop-2-enylpyrrolidine
• CAS: 1016983-72-4
• 化学式: C₁₄H₁₉N
• 分子量: 201.312
• InChiKey: NZHHIDPERZNZNK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  12
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  4-allyl-2-methyl-4-phenylpyrrolidine 、 苯甲酰氯 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成
  参考文献：
  名称：

  Zirconium Complexes Supported by Imidazolones: Synthesis, Characterization, and Application of Precatalysts for the Hydroamination of Aminoalkenes

  摘要：

  Dimeric zirconium benzyl and amide complexes supported by an imidazolone framework have been successfully synthesized and fully characterized. The amide complexes were found to be effective catalysts for intramolecular hydroamination of primary and secondary amines.

  DOI：

  10.1021/om100296m
• 作为产物：
  描述：

  2-allyl-2-phenylpent-4-en-1-amine 在 2-(1,3-bis(3'-butyl-imidazol-2'-ylidene)phenylene)(dimethylamido)dibromozirconium(IV) 作用下， 以 氘代甲苯 为溶剂， 反应 14.0h， 以98%的产率得到4-allyl-2-methyl-4-phenylpyrrolidine
  参考文献：
  名称：

  金属和卤素对未活化氨基烯烃加氢胺化/环化中速率影响的依赖性：CCC-NHC and和锆螯合物的合成，表征和催化速率

  摘要：

  使1,3-双（3'-丁基咪唑-1'-基）苯二溴化物（2b）或1,3-双（3'-丁基咪唑-1'-基）苯二氯化物（2c）反应Zr（NMe 2）4或Hf（NMe 2）4产生四个新的早期过渡金属CCC- N-杂环卡宾（CCC-NHC）钳形配合物。通过一种新方法合成了两种CCC-NHC钳形复合物，该复合物可实现室温反应，更短的反应时间以及略微更少的Zr（NMe 2）4或Hf（NMe 2）4。通过X射线晶体学测定了2-（1,3-双-3'-丁基咪唑-1'-基-2'-亚苯基）亚苯基）（二甲基氨基）（二溴）锆（IV）（3b）的分子结构。评价该复合物用于未活化的氨基烯烃的加氢胺化/环化，产生吡咯烷或哌啶。加氢胺化/环化速率取决于配合物中的卤素或金属。具有碘化物配体的配合物给出了最快的加氢胺化/环化速率（I> Br> Cl）。Zr配合物比Hf类似物提供更快的加氢胺化/环化速率。CCC-NHC ZrI 3络合物5的使用提高了反应速率。

  DOI：

  10.1016/j.jorganchem.2013.11.001

文献信息

• Metal and halogen dependence of the rate effect in hydroamination/cyclization of unactivated aminoalkenes: Synthesis, characterization, and catalytic rates of CCC-NHC hafnium and zirconium pincer complexes
  作者：Wesley D. Clark、Joon Cho、Henry U. Valle、T. Keith Hollis、Edward J. Valente

  DOI：10.1016/j.jorganchem.2013.11.001

  日期：2014.2

  (2c) was reacted with a stoichiometric amount of Zr(NMe2)4 or Hf(NMe2)4 yielding four new early transition metal CCC-N-heterocylic carbene (CCC-NHC) pincer complexes. Two of the CCC-NHC pincer complexes were synthesized via a new methodology, which allowed for a room temperature reaction, shorter reaction times, and slightly less Zr(NMe2)4 or Hf(NMe2)4. The molecular structure of 2-(1,3-bis-3′-butyl

  使1,3-双（3'-丁基咪唑-1'-基）苯二溴化物（2b）或1,3-双（3'-丁基咪唑-1'-基）苯二氯化物（2c）反应Zr（NMe 2）4或Hf（NMe 2）4产生四个新的早期过渡金属CCC- N-杂环卡宾（CCC-NHC）钳形配合物。通过一种新方法合成了两种CCC-NHC钳形复合物，该复合物可实现室温反应，更短的反应时间以及略微更少的Zr（NMe 2）4或Hf（NMe 2）4。通过X射线晶体学测定了2-（1,3-双-3'-丁基咪唑-1'-基-2'-亚苯基）亚苯基）（二甲基氨基）（二溴）锆（IV）（3b）的分子结构。评价该复合物用于未活化的氨基烯烃的加氢胺化/环化，产生吡咯烷或哌啶。加氢胺化/环化速率取决于配合物中的卤素或金属。具有碘化物配体的配合物给出了最快的加氢胺化/环化速率（I> Br> Cl）。Zr配合物比Hf类似物提供更快的加氢胺化/环化速率。CCC-NHC ZrI 3络合物5的使用提高了反应速率。
• CCC–N-heterocyclic carbene pincer complexes: Synthesis, characterization and hydroamination activity of a hafnium complex
  作者：Joon Cho、T. Keith Hollis、Edward J. Valente、Jaclyn M. Trate

  DOI：10.1016/j.jorganchem.2010.10.004

  日期：2011.1

  Our methodology for the stoichiometric preparation of CCC–NHC pincer complexes of Zr has been extended to Hf. The CCCBu–NHC pincer Hf complex has been characterized by X-ray crystal structure analysis. Catalytic activity in the intramolecular hydroamination/cyclization of unactivated alkenes is reported and compared to the recently reported Zr analog. An improved, scaled-up CuO-catalyzed aryl amination

  我们将化学计量制备Zr的CCC-NHC钳形络合物的方法扩展到了Hf，通过X射线晶体结构分析对CCC Bu- NHC的钳形Hf络合物进行了表征。报道了未活化的烯烃的分子内加氢/环化中的催化活性，并将其与最近报道的Zr类似物进行了比较。还报道了一种改进的按比例放大的CuO催化的1,3-二溴苯芳基胺化反应和一种用于制备双（丁基咪唑鎓）苯的成盐方法。
• An improved method for the synthesis of zirconium (CCC-N-heterocyclic carbene) pincer complexes and applications in hydroamination
  作者：Joon Cho、T. Keith Hollis、Theodore R. Helgert、Edward J. Valente

  DOI：10.1039/b805174g

  日期：——

  Upon heating Zr(NMe2)4, 1,3-bis(N-butyl-imidazolium)benzene diiodide and toluene analytically pure Zr pincer complex was obtained, which was found to be an intramolecular hydroamination catalyst.

  加热 Zr(NMe2)4、1,3-双（N-丁基咪唑鎓）苯二碘化物和甲苯后，得到了分析纯 Zr 钳子复合物，发现它是一种分子内氢化催化剂。
• Extreme π-Loading as a Design Element for Accessing Imido Ligand Reactivity. A CCC-NHC Pincer Tantalum Bis(imido) Complex: Synthesis, Characterization, and Catalytic Oxidative Amination of Alkenes
  作者：Theodore R. Helgert、Xiaofei Zhang、Hannah K. Box、Jason A. Denny、Henry U. Valle、Allen G. Oliver、Gopalakrishna Akurathi、Charles Edwin Webster、T. Keith Hollis

  DOI：10.1021/acs.organomet.6b00216

  日期：2016.10.24

  A rare Ta bis(imido) complex, which has unique reactivity, was prepared by manipulating the coordination sphere of a CCC-NHC pincer Ta complex. The reaction of lithium tert-butylamide with complex 1 yielded (1,3-bis(3'-butylimidazol-2'-yl-1'-idene)-2-phenylene)bis(tert-butylimido)tantalum(V) (2) as a lithium iodide bridged dimer, as determined by the X-ray structure. Complex 2 catalytically cyclized alpha,omega-aminoalkenes to effect an oxidative amination of alkenes (dehydrogenation by C-H activation) and produced a cyclic imine, an equivalent of reduced substrate, and varying proportions of hydroamination. Various additives and concentration impact the catalytic results. Computational and experimental observations have led to an initial mechanistic hypothesis. Based upon it, precatalyst 2 appears to be the first example of a bifunctional catalyst (MH-NHR) that is highly selective for nonpolar C-C bonds in preference to polar C-X bonds for outer-sphere hydrogenation.
• β-SiH-Containing Tris(silazido) Rare-Earth Complexes as Homogeneous and Grafted Single-Site Catalyst Precursors for Hydroamination
  作者：Naresh Eedugurala、Zhuoran Wang、KaKing Yan、Kasuni C. Boteju、Umesh Chaudhary、Takeshi Kobayashi、Arkady Ellern、Igor I. Slowing、Marek Pruski、Aaron D. Sadow

  DOI：10.1021/acs.organomet.6b00956

  日期：2017.3.27

  A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds LnN(SiHMe2)tBu}(3) (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1-3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln-H-Si interactions. These features are retained in solvent coordinated 2 center dot Et2O, 2 center dot THF, and 3 center dot THF. The change in spectroscopic features characterizing the secondary interactions (v(s1H), (1)J(siH)) from the unactivated SiH in the silazane HN(SiHMe2)tBu follows the trend 3 > 2 > 1 approximate to 2 center dot THF approximate to 3 center dot THF. Ligand lability follows the same pattern, with Et2O readily dissociating from 2 center dot Et2O while THF is displaced only during surface grafting reactions. I and 2 center dot THF graft onto mesoporous silica nanoparticles (MSN) to give LnN(SiHMe2)tBu}(n)@MSN (Ln = Sc (1@MSN), Y (2@MSN)) along with THF and protonated silazido as HN(SiHMe2)tBu and H(2)NtBu. The surface species are characterized by multinuclear and multidimensional solid-state (SS) NMR spectroscopic techniques, as well as diffuse reflectance FTIR, elemental analysis, and reaction stoichiometry. A key (1)J(SiH) SSNMR measurement reveals that the grafted sites most closely resemble Ln.THF adducts, suggesting that siloxane coordination occurs in grafted compounds. These species catalyze the hydroamination/bicyclization of aminodialkenes, and both solution-phase and interfacial conditions provide the bicyclized product with equivalent cis:trans ratios. Similar diastereoselectivities mediated by catalytic sites under the two conditions suggest similar effective environments.