N-(1-cyclohexylethylidene)benzylamine | 188645-15-0

• 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: N-(1-cyclohexylethylidene)benzylamine
• 英文别名: Benzenemethanamine, N-(1-cyclohexylethylidene)-；N-benzyl-1-cyclohexylethanimine
• CAS: 188645-15-0
• 化学式: C₁₅H₂₁N
• 分子量: 215.338
• InChiKey: AMIHDJXPWWQWRB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  12.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  N-(1-cyclohexylethylidene)benzylamine 在 三乙胺 作用下， 以 乙腈 、 苯 为溶剂， 反应 5.5h， 生成 cis-tert-Butyl benzyl(3-cyclohexyl-2-phenyloxetan-3-yl)carbamate
  参考文献：
  名称：

  The Paternò-Büchi Reaction of α-Alkyl-Substituted Enecarbamates and Benzaldehyde

  摘要：

  α-取代的邻炔氨基甲酸酯和烯酰胺5a-d、5f和6是通过两步反应从相应的酮、N-苄胺和适当的酰化试剂（Boc2O、Ac2O）制备的。苯甲醛与具有一级或二级烷基取代基的烯烃5a-d的[2+2]光环加成反应顺利进行，得到3-氨基氟烯烃8a-d，产率中等到良好（46-71%）。α-苯基取代的邻炔氨基甲酸酯5f未能生成光环加成产物，这可能是由于光激发的醛迅速发生能量转移（三重态敏化）。由于不太明显的原因，叔丁基取代的烯酰胺6在Paternò-Büchi反应中也未发生反应。所得到的3-烷基-3-氨基氟烯烃8是顺式和反式二叠体异构体的混合物。烷基取代基R的立体阻碍增强使得二叠体比率（cis-8/trans-8）向热力学更稳定的顺式产物移动（R = CH3时为29:71，R = 环己基时为57:43）。分离得到的氟烯烃二叠体cis-8a和trans-8a（R = CH3）在三氟乙酸处理下顺利发生开环/环化反应。氟烯烃trans-8a产生了氧杂二氢吡啶酮9和trans-10（92%），而氟烯烃cis-8a则专一获得氧杂二氢吡啶酮cis-10（54%）。

  DOI：

  10.1055/s-2001-15075
• 作为产物：
  描述：

  乙酰基环己烷 、 苄胺 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 N-(1-cyclohexylethylidene)benzylamine
  参考文献：
  名称：

  α-三烷基-α-叔胺的模块化光催化合成

  摘要：

  显示 α-三烷基-α-叔胺基序的分子提供了进入生物相关化学空间的重要和多功能领域的途径，但通过现有的合成方法难以进入。在这里，我们报告了一种操作简单的多组分方案，用于合成一系列功能和结构多样的 α-三烷基-α-叔胺，该方案利用三种容易获得的组分：二烷基酮、苄胺和烯烃。该策略依赖于使用可见光介导的光催化与现成的 Ir(III) 配合物，将全烷基酮亚胺物种单电子还原为 α-氨基自由基中间体；α-氨基自由基与多种烯烃进行 Giese 型加成，形成 α-三烷基-α-叔胺中心。该过程的机理被认为是通过整个氧化还原中性途径进行的，该途径涉及亚胺的光催化氧化还原中继，该亚胺由起始的胺-酮缩合产生，一直到亚胺衍生产物。这是可能的，因为中间支架中苄胺组分的存在驱动了 Giese 加成后的 1,5-氢原子转移步骤，形成稳定的苄基 α-氨基自由基，从而能够关闭光催化循环。这些研究详细介绍了反应平台的演变、对底物

  DOI：

  10.1021/jacs.1c07402

文献信息

• Asymmetric hydrogenation of N-alkyl and N-aryl ketimines using chiral cationic Ru(diamine) complexes as catalysts: the counteranion and solvent effects, and substrate scope
  作者：Fei Chen、Ziyuan Ding、Yanmei He、Jie Qin、Tianli Wang、Qing-Hua Fan

  DOI：10.1016/j.tet.2012.03.019

  日期：2012.7

  Asymmetric hydrogenation of N-alkyl and N-aryl ketimines catalyzed by chiral cationic η6-arene-(N-monosulfonylated diamine) Ru(II) complexes has been investigated. Strong counteranion and solvent effects on the enantioselectivity were observed. The ruthenium catalyst bearing non-coordinating BArF− anion was found to be particularly effective for the hydrogenation of acyclic and exocyclic N-alkyl ketimines

  的不对称氢化ñ -烷基和Ñ通过催化芳基酮亚胺的手性阳离子η 6 -arene-（Ñ -monosulfonylated二胺）的Ru（II）络合物进行了研究。观察到强烈的抗衡阴离子和溶剂对对映选择性的影响。钌催化剂轴承非配位BARF -阴离子被认为是对无环和环外的氢化特别有效ñ -烷基酮亚胺在（BOC）的存在下2O在二氯甲烷中或什至在无溶剂条件下提供的手性胺，其ee可达99％以上，并具有完全转化率。或者，在不存在（Boc）2 O的情况下，具有手性磷酸根阴离子和相应磷酸作为添加剂的钌催化剂也有效用于N-烷基酮亚胺的氢化，对映选择性和完全转化率优异。对于Ñ -芳基酮亚胺降低通过使用钌催化剂轴承BARF观察对映体过量-阴离子。因此，该催化方案为光学活性胺提供了简便实用的途径，并已成功用于对映体纯的（+）-舍曲林的克级合成中。
• Discovery of an iridacycle catalyst with improved reactivity and enantioselectivity in the hydrogenation of dialkyl ketimines
  作者：York Schramm、Fabiola Barrios-Landeros、Andreas Pfaltz

  DOI：10.1039/c3sc50587a

  日期：——

  Catalytically active iridacycles are formed by cyclometalation of acetophenone imines with Ir–PHOX complexes under hydrogen atmosphere. These complexes show unusually high reactivity and enantioselectivity in the hydrogenation of alkyl methyl ketimines. The structure of the cyclometalated imine has a strong effect on the conversion and enantiomeric excess.

  在氢气环境下，Ir-PHOX 复合物与苯乙酮亚胺发生环甲基化反应，形成了具有催化活性的铱环。在烷基甲基酮亚胺的氢化反应中，这些配合物显示出异常高的反应活性和对映选择性。环甲基化亚胺的结构对转化率和对映体过量有很大影响。
• Catalytic Asymmetric Hydrogenation of Imines with a Chiral Titanocene Catalyst: Scope and Limitations
  作者：Christopher A. Willoughby、Stephen L. Buchwald

  DOI：10.1021/ja00099a012

  日期：1994.10

  The asymmetric hydrogenation of imines with a chiral titanocene catalyst derived from Brintzinger's ansatitanocene complex 1 proceeds to afford amines with good to excellent enantioselectivity. The catalyst is particularly effective for the reduction of cyclic imines. For these substrates enantiomeric excesses from 95 to 99% were achieved. For acyclic imines lower enantiomeric excesses were observed. The reason for this is likely due to the fact that the acyclic imines are mixtures of anti and syn isomers which interconvert during the reaction. The catalyst was found to be tolerant of many functional groups found in organic synthesis. Thus the reaction represents an effective method for the synthesis of chiral cyclic amines.
• Chiral Molecular Tweezers: Synthesis and Reactivity in Asymmetric Hydrogenation
  作者：Markus Lindqvist、Katja Borre、Kirill Axenov、Bianka Kótai、Martin Nieger、Markku Leskelä、Imre Pápai、Timo Repo

  DOI：10.1021/ja512658m

  日期：2015.4.1

  We report the synthesis and reactivity of a chiral aminoborane displaying both rapid and reversible H-2 activation. The catalyst shows exceptional reactivity in asymmetric hydrogenation of enamines and unhindered imines with stereoselectivities of up to 99% ee. DFT analysis of the reaction mechanism pointed to the importance of both repulsive steric and stabilizing intermolecular non-covalent forces in the stereodetermining hydride transfer step of the catalytic cycle.
• Catalytic Asymmetric Hydrogenation of Imines with a Chiral Titanocene Catalyst: Kinetic and Mechanistic Investigations
  作者：Christopher A. Willoughby、Stephen L. Buchwald

  DOI：10.1021/ja00105a011

  日期：1994.12

  A kinetic study of the asymmetric titanocene-catalyzed imine hydrogenation has revealed the rate law to be rate = k(obs)[Ti][H-2]. for cyclic imine 2 and acyclic imine 4. This rate law is consistent with a mechanism in which the imine reacts with a titanium hydride in a fast 1,2-insertion step, to form a titanium amide intermediate, followed by slow reaction of the amide complex with hydrogen to produce the amine and regenerate the titanium hydride. Labeling studies for the hydrogenation of 2 and studies using enantiomerically enriched aldimine 6 indicate that beta-H elimination is also slow, relative to hydrogenolysis, for both 2 and 4. The enantiomeric excesses for the hydrogenation of 2 were found to be essentially insensitive to changes in reaction conditions. However, for imine 4, the ee's were dependent on several variables, most significantly hydrogen pressure. This-phenomenon has been explained on the basis of the interconversion of the syn and anti isomers of 4 during the hydrogenation. It has been shown that syn-4 reacts faster than anti-4, a necessary condition for the explanation presented to hold true. A stereochemical model based on steric and electronic considerations has been proposed to account for the observed selectivity. This model can aid in predicting the absolute configurations of the amines farmed in this process.