1-benzyl-2-methyl-4-phenylpyrrolidine | 1370583-88-2

• 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: 1-benzyl-2-methyl-4-phenylpyrrolidine
• 英文别名: 1-Benzyl-2-methyl-4-phenylpyrrolidine
• CAS: 1370583-88-2
• 化学式: C₁₈H₂₁N
• 分子量: 251.371
• InChiKey: PZLZTYNMWPHYTC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  3.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  N-benzyl-2-phenylpent-4-en-1-amine 在 C₆₇H₇₇IrN₂⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 作用下， 以 二氯甲烷-D2 为溶剂， 以90%的产率得到1-benzyl-2-methyl-4-phenylpyrrolidine
  参考文献：
  名称：

  开发用于高效对映选择性分子内氢化反应的NHC-铱催化剂

  摘要：

  引入手性阳离子NHC-铱络合物作为未活化氨基烯烃的分子内加氢胺化反应的催化剂。所述催化剂在吡咯烷的构造中显示出高活性，其以优异的光学纯度被获得。还生产了对映体富集的哌啶和二氢吲哚，该LTM系统可耐受各种官能团。提出了一种反应机理，并提出和讨论了这些催化剂的主要失活途径。

  DOI：

  10.1021/acscatal.7b02508

文献信息

• Synthetic and Computational Studies on the Rhodium-Catalyzed Hydroamination of Aminoalkenes
  作者：Alexandra E. Strom、David Balcells、John F. Hartwig

  DOI：10.1021/acscatal.6b01320

  日期：2016.9.2

  The influence of ligand structure on rhodium-catalyzed hydroamination has been evaluated for a series of phosphinoarene ligands. These catalysts have been evaluated in a set of catalytic intramolecular Markovnikov hydroamination reactions. The mechanism of hydroamination catalyzed by the rhodium(I) complexes in this study was examined computationally, and the turnover-limiting step was elucidated.

  对于一系列膦基芳烃配体，已经评估了配体结构对铑催化的加氢胺化的影响。这些催化剂已经在一系列分子内马尔可夫尼可夫氢化反应中进行了评估。通过计算研究了铑（I）配合物催化加氢胺化的机理，并阐明了限制营业额的步骤。这些计算研究被扩展到一系列理论上的氢化胺化催化剂，以比较辅助配体取代基的电子效应。将中间体和过渡态的相对能与未取代催化剂催化的反应中的中间体的相对能进行了比较。将富电子和贫电子催化剂的反应性的实验差异与计算结果进行了比较，并且发现从反应势垒预测的电子贫乏催化剂的活性被高估了。因此，与未取代的配体相比，本研究中对催化剂的分析扩展到包括每个配体的结合偏好。该信息说明了观察到的反应性与计算得出的电子贫乏配体的总反应势垒之间的差异。计算了对于新的配体结构的配体结合偏好，并且预测了与铑生成的催化剂强烈结合的配体，用于实验催化反应，其反应性比预计的结合较弱的反应性更高。与未取代的配体相比，本研究中对
• Unusual NHC–Iridium(I) Complexes and Their Use in the Intramolecular Hydroamination of Unactivated Aminoalkenes
  作者：Gellért Sipos、Arnold Ou、Brian W. Skelton、Laura Falivene、Luigi Cavallo、Reto Dorta

  DOI：10.1002/chem.201600378

  日期：2016.5.10

  N‐heterocyclic carbene (NHC) ligands with naphthyl side chains were employed for the synthesis of unsaturated, yet isolable [(NHC)Ir(cod)]+ (cod=1,5‐cyclooctadiene) complexes. These compounds are stabilised by an interaction of the aromatic wingtip that leads to a sideways tilt of the NHC−Ir bond. Detailed studies show how the tilting of such N‐heterocyclic carbenes affects the electronic shielding

  具有萘基侧链的N-杂环卡宾（NHC）配体用于合成不饱和但可分离的[（NHC）Ir（cod）] +（cod = 1,5-环辛二烯）配合物。这些化合物通过芳族翼尖的相互作用而稳定，从而导致NHC-Ir键的侧向倾斜。详细的研究表明，此类N杂环卡宾的倾斜如何影响卡宾碳原子的电子屏蔽性能，以及13 C NMR信号中的明显高场位移如何反映出这种情况。当用于分子内加氢胺化时，这些[（NHC）Ir（cod）] +在温和的反应条件下，这些物种显示出很高的催化活性。对映体纯的催化剂体系可产生具有出色对映选择性的吡咯烷。
• A N-heterocyclic carbene (NHC) platinum complex as pre-catalyst for the intramolecular hydroamination of olefins with secondary alkylamines and oxidative amination of ω-alkenic amines
  作者：Rui Zhang、Qin Xu、Liang-yong Mei、Sheng-ke Li、Min Shi

  DOI：10.1016/j.tet.2012.02.060

  日期：2012.4

  A N-heterocyclic carbene (NHC) platinum complex 3 prepared from BINAM was found to be a highly effective pre-catalyst for the intramolecular hydroamination of olefins with secondary alkylamines to give the corresponding intramolecular hydroamination products in excellent yields. The substrate scope has been carefully examined and the plausible reaction mechanism has been also proposed. (C) 2012 Elsevier Ltd. All rights reserved.
• In-Depth Study on Chloride Abstractions from (NHC)Ir(COD)Cl Complexes
  作者：Gellért Sipos、Pengchao Gao、Daven Foster、Brian W. Skelton、Alexandre N. Sobolev、Reto Dorta

  DOI：10.1021/acs.organomet.6b00864

  日期：2017.2.27

  While attempting to prepare a series of cationic NHC-Ir complexes of general formula [(NHC)Ir(COD)](+) via the silver salt metathesis reaction of its precursor (NHC)Ir(COD)Cl in dichloromethane, we unexpectedly synthesized [(mu-Cl)(2,7-SICyNap)Ir(COD))center dotAg(OTf)}], a chlotide-bridged Ir-Ag adduct. This result led us to investigate the chloride abstraction from the (NHC)Ir(COD)Cl systein in detail. We show how the outcome of this ubiquitous reaction is dependent on a fine balance between the nucleophilicity of the weakly coordinating anion (WCA) and the polarity/coordinating ability of the reaction medium. A frequently encountered alternative to using silver salts is also presented and compared. The experimental difference in the reactivitieS of cationic catalysts in a representative intramolecular hydroamination reaction shows how a cationic Ir-Ag adduct can fail to deliver the reaction product through what appears to be a stabilization of the catalytically inactive iridium-silver intermediate by the educt.
• Developing NHC-Iridium Catalysts for the Highly Efficient Enantioselective Intramolecular Hydroamination Reaction
  作者：Pengchao Gao、Gellért Sipos、Daven Foster、Reto Dorta

  DOI：10.1021/acscatal.7b02508

  日期：2017.9.1

  introduced as catalysts for the intramolecular hydroamination reaction of unactivated aminoalkenes. The catalysts show high activity in the construction of pyrrolidines, which are accessed with excellent optical purity. Enantiomerically enriched piperidines and indolines are also produced, and various functional groups are tolerated with this LTM system. A reaction mechanism is proposed, and a major

  引入手性阳离子NHC-铱络合物作为未活化氨基烯烃的分子内加氢胺化反应的催化剂。所述催化剂在吡咯烷的构造中显示出高活性，其以优异的光学纯度被获得。还生产了对映体富集的哌啶和二氢吲哚，该LTM系统可耐受各种官能团。提出了一种反应机理，并提出和讨论了这些催化剂的主要失活途径。