(R)-4-methoxy-N-(octan-2-yl)aniline

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (R)-4-methoxy-N-(octan-2-yl)aniline
• 英文别名: 4-methoxy-N-[(2R)-octan-2-yl]aniline
• 化学式: C₁₅H₂₅NO
• 分子量: 235.37
• InChiKey: UTLSYIVGBGPJOP-CYBMUJFWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.2
• 重原子数：
  17
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  仲辛酮 在 四氢吡咯 、 rac-(ethylene-1,2-bis(4,5,6,7-tetrahydro-1-indenyl))TiF₂ polymethylhydrosiloxane 、 苯硅烷 、 异丁胺 作用下， 以 甲醇 、 甲苯 为溶剂， 反应 13.0h， 生成 (R)-4-methoxy-N-(octan-2-yl)aniline
  参考文献：
  名称：

  A Method for the Asymmetric Hydrosilylation of N-Aryl Imines

  摘要：

  [GRAPHICS]The asymmetric reduction of N-aryl imines to yield chiral amines with enantiomeric excesses above 90% was achieved. Ethylenebis(eta(5)-tetrahydroindenyl)titanium difluoride ((EBTHI)TiF2, 1) was employed as the precatalyst with polymethylhydrosiloxane (PMHS) as the stoichiometric reducing agent. A variety of N-aryl imines derived from nonaromatic ketones were reduced with high ee.

  DOI：

  10.1021/ol005583w

文献信息

• Asymmetric Transfer Hydrogenation of Ketimines by Indoline as Recyclable Hydrogen Donor
  作者：Kodai Saito、Hiromitsu Miyashita、Takahiko Akiyama

  DOI：10.1021/ol502486f

  日期：2014.10.17

  The chiral phosphoric acid catalyzed enantioselective transfer hydrogenation of various ketimines was achieved by the use of 2-aryl indoline as the hydrogen donor. Corresponding chiral amines were obtained in good chemical yields with excellent enantioselectivities.

  通过使用2-芳基二氢吲哚作为氢供体，实现了各种酮亚胺的手性磷酸催化的对映选择性转移氢化。以良好的化学产率和优异的对映选择性获得了相应的手性胺。
• Enantioselective organocatalytic reductive amination of aliphatic ketones by benzothiazoline as hydrogen donor
  作者：Kodai Saito、Takahiko Akiyama

  DOI：10.1039/c2cc31486j

  日期：——

  The chiral phosphoric acid-catalyzed enantioselective reductive amination of aliphatic ketones with aromatic amines was successfully achieved by the use of benzothiazoline as the hydrogen donor. Corresponding chiral aliphatic amines were obtained with excellent enantioselectivities.

  通过使用苯并噻唑啉作为氢供体成功地实现了脂肪族酮与芳香族胺的手性磷酸催化对映选择性还原胺化反应。得到具有优良对映选择性的相应的手性脂族胺。
• Catalytic Enantioselective Amination of Alcohols by the Use of Borrowing Hydrogen Methodology: Cooperative Catalysis by Iridium and a Chiral Phosphoric Acid
  作者：Yao Zhang、Ching-Si Lim、Derek Sui Boon Sim、Hui-Jie Pan、Yu Zhao

  DOI：10.1002/anie.201307789

  日期：2014.1.27

  synthesis of chiral amines, with reductants ranging from Hantzsch esters, silanes, and formic acid to H2 gas. Alternatively, the amination of alcohols by the use of borrowing hydrogen methodology has proven a highly atom economical and green method for the production of amines without an external reductant, as the alcohol substrate serves as the H2 donor. A catalytic enantioselective variant of this

  酮亚胺的催化不对称还原已经广泛地用于手性胺的合成，还原剂的范围从汉茨（Hantzsch）酯，硅烷和甲酸到H 2气体。或者，由于使用醇底物作为H 2，通过借用氢方法进行的醇胺化已被证明是一种高度原子经济且绿色的方法，无需外部还原剂即可生产胺。捐赠者。然而，用于合成手性胺的该方法的催化对映选择性变体是未知的。我们已经研究了由不对称氢化反应已知的手性配体所支持的各种过渡金属配合物，以及手性布朗斯台德酸，它们被证明对于亚胺中间体的形成和转移加氢步骤至关重要。我们的研究导致了醇的不对称胺化，从而提供了具有良好或优异的对映选择性的多种手性胺。
• Chiral (cyclopentadienone)iron complexes with a stereogenic plane as pre-catalysts for the asymmetric hydrogenation of polar double bonds
  作者：Xishan Bai、Mattia Cettolin、Giulia Mazzoccanti、Marco Pierini、Umberto Piarulli、Valentina Colombo、Alberto Dal Corso、Luca Pignataro、Cesare Gennari

  DOI：10.1016/j.tet.2019.01.057

  日期：2019.3

  easy-to-prepare chiral (cyclopentadienone)iron pre-catalysts for enantioselective CO and CN hydrogenations. Starting from readily accessible achiral materials, six chiral (cyclopentadienone)iron complexes (1a-f) possessing a stereogenic plane were synthesized in racemic form. Based on the screening of pre-catalysts (±)-1a-f in the hydrogenation of ketones and ketimines, we selected two complexes (1a and 1d)

  在本文中，我们描述了一个易于制备的手性（环戊二烯酮）铁预催化剂小库，用于对映选择性的C O和C N加氢。从易于获得的非手性材料开始，以消旋形式合成了六个具有立体生成平面的手性（环戊二烯酮）铁配合物（1a-f）。基于在酮和酮亚胺加氢中筛选前催化剂（±）-1a-f，我们选择了两种配合物（1a和1d）用于半制备对映选择性HPLC拆分。通过XRD分析确定1a和1d分离的对映体的绝对构型（1a），并通过实验和DFT计算的ECD和ORD光谱进行比较（1d）。对映体纯催化剂（S）-1a和（R）-1d在几种酮和酮的不对称氢化中进行了测试，显示出良好的活性和适度的对映选择性，ee值从非常低到中等（54％）。
• Asymmetric Reductive Amination with Pinacolborane Catalyzed by Chiral SPINOL Borophosphates
  作者：Zhenwei Wu、Hualing He、Minglei Chen、Linfei Zhu、Weitao Zheng、Yang Cao、Jon C. Antilla

  DOI：10.1021/acs.orglett.2c03866

  日期：2022.12.30

  The catalytic asymmetric reductive amination of ketones with pinacolborane employing chiral SPINOL-derived borophosphates as catalysts has been realized. A series of chiral amine derivatives bearing multiple functional groups were obtained in good to excellent yields and enantioselectivities (up to 97% yield, 98% ee) under mild reaction conditions. Moreover, the synthetic applicability of the established

  使用手性 SPINOL 衍生的硼磷酸盐作为催化剂，酮与频哪醇硼烷的催化不对称还原胺化反应已经实现。在温和的反应条件下，获得了一系列具有多个官能团的手性胺衍生物，具有良好至优异的产率和对映选择性（高达 97% 产率，98% ee）。此外，该方法的合成适用性已通过 ( R )-Fendiline 的不对称合成得到证明。