(R)-2'-methyl-[1,1'-binaphthalen]-2-amine

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (R)-2'-methyl-[1,1'-binaphthalen]-2-amine
• 英文别名: 1-(2-Methylnaphthalen-1-yl)naphthalen-2-amine
• 化学式: C₂₁H₁₇N
• 分子量: 283.373
• InChiKey: QIDDOECWNUEZDC-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  22
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.05
• 拓扑面积：
  26
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (R)-2'-methyl-[1,1'-binaphthalen]-2-amine 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 三乙胺 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 22.0h， 生成
  参考文献：
  名称：

  通过手性双功能硫化物催化溴内酯化对 α-季羧酸进行非酶促动力学拆分和去对称化

  摘要：

  外消旋羧酸的动力学拆分是对映选择性制备手性羧酸的可靠方法。尽管已经报道了手性 α-叔羧酸的有效催化动力学拆分，但带有全碳四元立体中心的 α-季羧酸的动力学拆分仍然是一项艰巨的挑战。在此，我们报告了通过手性双官能硫化物催化炔烃溴内酯化反应动力学拆分 α-季铵酸的一个宝贵例子。通过非手性 α,α-二炔丙基羧酸的催化对映选择性去对称溴内酯化反应，评估了手性硫化物识别 α-季铵羧酸的能力，这是一种与目标动力学分辨率相关的反应。

  DOI：

  10.1246/bcsj.20210347
• 作为产物：
  描述：

  (R)-N-benzyl-2'-methyl-[1,1'-binaphthyl]-2-amine 在 palladium 10% on activated carbon 、 氢气 作用下， 以 乙酸乙酯 为溶剂， 40.0 ℃ 、101.33 kPa 条件下， 反应 84.0h， 以0.542 g的产率得到(R)-2'-methyl-[1,1'-binaphthalen]-2-amine
  参考文献：
  名称：

  具有手性联萘基骨架的分子内硫稳定的硅阳离子：三种不同基序的合成及其在对映选择性Diels-Alder反应中的应用

  摘要：

  The formation and Si-29 NMR spectroscopic characterization of silicon cations that are intramolecularly stabilized by a dialkeyl thioether are described. The chemical stability of the silicon sulfur Lewis pair and, hence, the viability Of the approach, were probed with a 2-[(alkylthio)methyl]phenyl-substituted hydrosilane as a proxy before three different motifs with chiral binaphthyl backbones were prepared in multistep sequences. The degree of shielding of the silicon atom in these cations was found to depend on the substitution pattern at the silicon atom and the ring size generated by the silicon sulfur interaction: These sulfur-stabilized silicon cations are sufficiently reactive to promote Diels-Alder reactions of cyclohexa-1,3-diene with various dienophiles; the same set of reactions with cyclopentadiene is also reported. One of the three chiral Lewis acids induces low, but promising, enantioselectivity, and 24% ee is the highest Value so far obtained with a cationic tetracoordinate silicon catalyst.

  DOI：

  10.1021/acs.organomet.5b00351

文献信息

• Switchable Smiles Rearrangement for Enantioselective <i>O</i>-Aryl Amination
  作者：Xihao Chang、Qinglin Zhang、Chang Guo

  DOI：10.1021/acs.orglett.9b01848

  日期：2019.6.21

  atropisomeric anilines from abundant and readily available precursors is one of the most challenging but valuable processes in organic synthesis. The use of highly efficient Smiles rearrangement to accomplish switchable enantioselective amination reactions of O-arenes provides access to nonsymmetric 2′-amino[1,1′-binaphthalen]-2-ol (i.e., NOBIN-type) and [1,1′-binaphthalene]-2,2′-diamine (i.e., BINAM-type)

  由丰富且容易获得的前体组成的对映异构体苯胺的不对称组装是有机合成中最具挑战性但最有价值的过程之一。使用高效的Smiles重排完成O-芳烃的可切换对映选择性胺化反应，可得到非对称的2'-氨基[1,1'-双萘] -2-ol（即NOBIN型）和[1,1' -双萘] -2,2'-二胺（即BINAM型）衍生物。这种无过渡金属的策略提供了一种强大的途径，可以访问各种先进的高度功能化的对映体丰富的苯胺。
• Design of Chiral Bifunctional Dialkyl Sulfide Catalysts for Regio‐, Diastereo‐, and Enantioselective Bromolactonization
  作者：Ryuichi Nishiyori、Ayano Tsuchihashi、Ayaka Mochizuki、Kazuma Kaneko、Masahiro Yamanaka、Seiji Shirakawa

  DOI：10.1002/chem.201803703

  日期：2018.11.13

  effective chiral dialkyl sulfide organocatalysts remain relatively rare and under‐developed, despite the potential utility of dialkyl sulfide catalysts. Herein, we report the development of chiral bifunctional dialkyl sulfide catalysts possessing a urea moiety for regio‐, diastereo‐, and enantioselective bromolactonization. The importance of the bifunctional design of chiral sulfide catalysts was clearly

  尽管已经开发出多种用于不对称转化的手性有机催化剂，但是尽管有潜在的实用性，但有效的手性二烷基硫醚有机催化剂仍然相对较少且开发不足。本文中，我们报道了具有脲部分的手性双官能二烷基硫醚催化剂的开发，该脲部分用于区域，非对映和对映选择性溴内酯化。手性硫化物催化剂的双功能设计的重要性在本工作中得到了明确证明。根据实验和理论研究的结果，阐明了催化剂的硫化物和脲部分的作用。
• Catalyst-Controlled Regio- and Stereoselective Bromolactonization with Chiral Bifunctional Sulfides
  作者：Ayano Tsuchihashi、Seiji Shirakawa

  DOI：10.1055/s-0037-1610716

  日期：2019.9

  Highly regioselective 5-exo bromolactonizations of stilbene-type carboxylic acids bearing electron-withdrawing substituents are achieved for the first time via the use of chiral bifunctional sulfide catalysts possessing a urea moiety. The chiral phthalide products are obtained in moderate to good enantioselectivities as the result of 5-exo cyclizations.

  通过使用具有尿素部分的手性双功能硫化物催化剂，首次实现了具有吸电子取代基的二苯乙烯型羧酸的高度区域选择性 5-外溴内酯化。作为 5-exo 环化的结果，手性苯酞产物以中等至良好的对映选择性获得。
• A Versatile Method for Kinetic Resolution of Protecting‐Group‐Free BINAMs and NOBINs through Chiral Phosphoric Acid Catalyzed Triazane Formation
  作者：Wei Liu、Qianwen Jiang、Xiaoyu Yang

  DOI：10.1002/anie.202009395

  日期：2020.12.21

  azodicarboxylates. A series of mono‐N‐protected and unprotected BINAMs, diphenyl diamines and NOBIN derivatives could be kinetically resolved with excellent performances (with s factor up to 420). The gram‐scale reactions and facile derivatizations of the chiral products demonstrate the potential of these methods in the asymmetric synthesis of chiral catalysts and ligands.

  通过手性磷酸与偶氮二羧酸酯催化三氮烷的形成，已实现了无保护基的BINAM和NOBIN的通用动力学拆分。一系列具有单-N-保护和未保护的BINAM，二苯二胺和NOBIN衍生物可以动力学拆分，并具有出色的性能（系数高达420）。手性产物的克级反应和易衍生化证明了这些方法在手性催化剂和配体的不对称合成中的潜力。
• Intramolecularly Sulfur-Stabilized Silicon Cations with Chiral Binaphthyl Backbones: Synthesis of Three Different Motifs and Their Application in Enantioselective Diels–Alder Reactions
  作者：Volker H. G. Rohde、Maria F. Müller、Martin Oestreich

  DOI：10.1021/acs.organomet.5b00351

  日期：2015.7.13

  The formation and Si-29 NMR spectroscopic characterization of silicon cations that are intramolecularly stabilized by a dialkeyl thioether are described. The chemical stability of the silicon sulfur Lewis pair and, hence, the viability Of the approach, were probed with a 2-[(alkylthio)methyl]phenyl-substituted hydrosilane as a proxy before three different motifs with chiral binaphthyl backbones were prepared in multistep sequences. The degree of shielding of the silicon atom in these cations was found to depend on the substitution pattern at the silicon atom and the ring size generated by the silicon sulfur interaction: These sulfur-stabilized silicon cations are sufficiently reactive to promote Diels-Alder reactions of cyclohexa-1,3-diene with various dienophiles; the same set of reactions with cyclopentadiene is also reported. One of the three chiral Lewis acids induces low, but promising, enantioselectivity, and 24% ee is the highest Value so far obtained with a cationic tetracoordinate silicon catalyst.