(R)-N-(1-methyl-2-methoxyethyl)-2,6-dimethylaniline | 118604-66-3

• 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: (R)-N-(1-methyl-2-methoxyethyl)-2,6-dimethylaniline
• 英文别名: N-(1-methoxy-2-propyl)-2,6-dimethylaniline；(R)-N-(1-methoxypropan-2-yl)-2,6-dimethylaniline；N-[(2R)-1-methoxypropan-2-yl]-2,6-dimethylaniline
• CAS: 118604-66-3
• 化学式: C₁₂H₁₉NO
• 分子量: 193.289
• InChiKey: QYJCGOLBBQDWFE-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  21.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  methyl 2-(2,6-dimethylphenylamino)propanoate 在 lithium aluminium tetrahydride 、 potassium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 6.0h， 生成 (R)-N-(1-methyl-2-methoxyethyl)-2,6-dimethylaniline
  参考文献：
  名称：

  与（S）-甲草胺工艺有关的铱-亚胺和-胺配合物：结构，交换动力学和Iri引起外消旋作用的CH活化。

  摘要：

  DMA-亚胺[2,6-二甲基苯基-1'-甲基-2'-甲氧基乙基亚胺，1 a）和（R）-DMA-胺[（1'R）-2,6-二甲基苯基-1'-合成了先正达（S）-甲草胺工艺的催化亚胺加氢步骤相关的甲基2'-甲氧基乙胺2a]：[Ir2Cl2（cod）2]（cod = 1,5-cyclooctadiene）的易位交换与[Ag（1a）2] BF4和[Ag（（R-2-2 a）2] BF4一起提供[Ir（cod）（kappa2- -1 a）] BF4（11）和[Ir（cod）（kappa2 -（R）-2 a）] BF4（（R-19-19））。然后将这些配合物用于流阻实验中，以研究胺2a被亚胺1a从配合物19置换而形成亚胺配合物11的过程，从而对催化循环中的产物/底物交换步骤进行建模。数据表明了两步关联机制，其特征为k1 =（2.6 +/- 0.3）x 10（2）M（-1）s（-1）和k2 =（4。3 +/-

  DOI：

  10.1002/chem.200306008

文献信息

• Chiral phosphine-phosphoramidite ligands for highly enantioselective hydrogenation of N-arylimines
  作者：Qing Li、Chuan-Jin Hou、Xiao-Ning Liu、De-Zhi Huang、Yan-Jun Liu、Rui-Feng Yang、Xiang-Ping Hu

  DOI：10.1039/c4ra16062b

  日期：——

  The asymmetric hydrogenation of N-arylimines with the chiral phosphine-phosphoramidite ligand, (Sc,Sa)-PEAPhos 2b, has been developed. The results revealed that the presence of the substituents on the 3,3′-positions of the binaphthyl backbone significantly improved the enantioselectivity. The utility of this methodology was demonstrated in the synthesis of the chiral fungicide (R)-metalaxyl.

  已经开发了具有手性膦-亚磷酰胺配体（S c，S a）-PEAPhos 2b的N-芳基丙氨酸的不对称氢化。结果表明，在联萘骨架的3，3'-位置上的取代基的存在显着提高了对映选择性。该方法的实用性在手性杀菌剂（R）-甲霜灵的合成中得到了证明。
• Chiral Phosphine–Phosphoramidite Ligands for Highly Efficient Ir-Catalyzed Asymmetric Hydrogenation of Sterically Hindered <i>N</i>-Arylimines
  作者：Chuan-Jin Hou、Ya-Hui Wang、Zhuo Zheng、Jie Xu、Xiang-Ping Hu

  DOI：10.1021/ol301618r

  日期：2012.7.6

  A mild and general iridium-catalyzed, highly enantioselective hydrogenation of sterically hindered N-arylimines with a new H8-BINOL-derived phosphine–phosphoramidite ligand has been developed. The present catalytic system features high turnover numbers (up to 100000) and good to perfect enantioselectivities (up to 99% ee) for the hydrogenation of a variety of sterically hindered N-arylimines.

  已经开发出一种温和的，铱催化的，具有新的H 8 -BINOL衍生的膦-亚磷酰胺配体的空间受阻的N-芳胺类化合物的高对映体选择性氢化。本催化体系的特征在于用于多种空间受阻的N-芳基丙氨酸的氢化的高周转数（高达100000）和良好至完美的对映选择性（高达99％ee）。
• Chiral organic catalysts for the stereoselective reduction of carbon-nitrogen double bonds for the preparation of enantiomerically enriched amines
  申请人：UNIVERSITA' DEGLI STUDI DI MILANO

  公开号：EP2065371A1

  公开（公告）日：2009-06-03

  The invention relates to compounds of general formula (I): wherein R1-R7 are as defined in the description for use as catalysts in the stereoselective reduction of imines in the presence of trichlorosilane as reducing agent.

  本发明涉及一般式(I)的化合物：其中R1-R7如描述中定义，用作催化剂，存在三氯硅烷还原剂的情况下进行亚胺的立体选择性还原。
• Chiral poisoning of rac-diop iridium complexes in the catalytic enantioselective hydrogenation of imines
  作者：Rafael Sablong、John A. Osborn、J.W. Faller

  DOI：10.1016/s0022-328x(96)06624-7

  日期：1997.1

  efficient catalysts for the enantioselective hydrogenation of imines. In the present study we have prepared the analogues using rac-diop. Among the possible dimers, there was only a slight preference for the μ-I2 heterodimer [Ir(R,R)-ddiopHI2][Ir(S,S)-diopHI2]}. Although this mixture of dimers was a moderately good catalyst for the hydrogenation of imines, it showed no enantioselectivity, as expected

  二聚体Ir（III）络合物[Ir（PP）HI 2 ] 2（PP =对映纯生物磷s）先前已被证明是亚胺对映选择性氢化的有效催化剂。在本研究中，我们使用rac -diop制备了类似物。在可能的二聚体，只有对μ-I的轻微偏爱2异源二聚体物[Ir（[R ，- [R）-ddiopHI 2 ]的[Ir（小号，小号）-diopHI 2 ]}。尽管这种二聚体混合物对于亚胺的氢化是中等良好的催化剂，但没有显示出预期的对映选择性。易于获得的氨基膦次膦酸酯配体（+）-（S）-pronop，以[（S）-pronop]：[Ir] tot = 1：1的比例与该二聚体混合物产生不良的催化剂，该催化剂在100h内仅产生了很少的周转。然而，以[（S）-pronop]：[Ir] tot＝ 1∶2的比例向该二聚体混合物中添加（+）-（S）-nonop产生了亚胺的对映选择性氢化的有效催化剂。由非外消旋二重奏制备的二聚体在催化中未观察到明显的手性扩增。
• Chiral Lewis base promoted trichlorosilane reduction of ketimines. An enantioselective organocatalytic synthesis of chiral amines
  作者：Stefania Guizzetti、Maurizio Benaglia、Franco Cozzi、Rita Annunziata

  DOI：10.1016/j.tet.2009.06.015

  日期：2009.8

  The reduction of the carbon-nitrogen double bond is an important transformation. Here we report our studies on a family of chiral organic catalysts able to promote the stereoselective reduction of ketimines with trichlorosilane. The very cheap, metal-free catalysts were easily prepared in one step from commercially available products, namely a chiral aminoalcohol and picolinic acid derivatives. The catalyst structure was extensively modified in a study that allowed to identify an extremely active species, able to promote the reduction on a large variety of substrates with high efficiency (up to 95% ee). A three component methodology has been also developed, where the enantiomerically enriched amine was isolated after performing the reaction by mixing a ketone and an amine in the presence of trichlorosilane and the catalyst. Its synthetic potentiality was demonstrated by employing the present metal-free catalytic procedure in the preparation of (S)-metolachlor, a potent and widely used herbicide. (C) 2009 Elsevier Ltd. All rights reserved.