7-(4-nitrobenzoyl)-7-azabicyclo<4.1.0>heptane

• 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: 7-(4-nitrobenzoyl)-7-azabicyclo<4.1.0>heptane
• 英文别名: 1,2-cyclohexane；meso-7-(4-nitrobenzoyl)-7-azabicyclo[4.1.0]heptane；7-(4-nitrobenzoyl)-7-azabicyclo[4.1.0]heptane；N-(4-nitrobenzoyl)-7-azabicyclo[4.1.0]heptane；[(1S,6R)-7-azabicyclo[4.1.0]heptan-7-yl]-(4-nitrophenyl)methanone
• 化学式: C₁₃H₁₄N₂O₃
• 分子量: 246.266
• InChiKey: HXRCYLFJYYZKNV-ONXXMXGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  18
• 可旋转键数：
  1
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  65.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  7-(4-nitrobenzoyl)-7-azabicyclo<4.1.0>heptane 在 lithium aluminium tetrahydride 、 diethylzinc 、 二环己基酒石酸酯 、 溶剂黄146 、 sodium nitrite 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 42.0h， 生成 (1S,2S)-2-(naphthalene-2-ylsulfanyl)cyclohexanol
  参考文献：
  名称：

  酒石酸二烷基酯-二乙基锌配合物催化对称的N-酰基氮丙啶与硫醇的不对称开环反应

  摘要：

  在由二乙基锌和L-（+）-酒石酸二烷基酯制备的手性锌络合物的存在下，进行1,2-（N-酰基亚氨基）环己烷（N-酰基环丙啶）与一些硫醇的不对称开环反应，得到反式2-（N-酰基氨基）-1-芳基硫代环己烷的ee最高可达93％。对映选择性很大程度上受反应物的摩尔比和手性酒石酸二烷基酯的性质的影响。L-（+）-酒石酸锌-二烷基络合物的化学结构通过1 H NMR光谱和分子量进行了讨论。

  DOI：

  10.1016/0040-4020(96)00370-5
• 作为产物：
  描述：

  cis-7-tosyl-7-azabicyclo[4.1.0]heptane 在 sodium naphthalenide 作用下， 以 乙二醇二甲醚 为溶剂， 反应 12.25h， 生成 7-(4-nitrobenzoyl)-7-azabicyclo<4.1.0>heptane
  参考文献：
  名称：

  Scalable Synthesis of N-Acylaziridines from N-Tosylaziridines

  摘要：

  N-Acylaziridines are important starting materials for the synthesis of chiral amine derivatives. The traditional methods for producing these activated aziridines have significant drawbacks. The gram scale synthesis of N-acylaziridines by deprotection of N-tosylaztridines and reprotection with N-hydroxysuccinimide derivatives is described. Mono- and disubstituted aziridines perform well, with complete retention of stereochemical purity. The consistently moderate yields are linked to the N-tosylaziridine deprotection step, while acylation with N-hydroxysuccinimide derivatives is highly efficient.

  DOI：

  10.1021/jo401267j

文献信息

• Key Role of the Lewis Base Position in Asymmetric Bifunctional Catalysis:  Design and Evaluation of a New Ligand for Chiral Polymetallic Catalysts
  作者：Ikuo Fujimori、Tsuyoshi Mita、Keisuke Maki、Motoo Shiro、Akihiro Sato、Sanae Furusho、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja067003h

  日期：2006.12.1

  system should be generated. Synthesis of these ligands is simple and high yielding, using a catalytic dynamic kinetic resolution promoted by the Trost catalyst as a key step. Ligand function was assessed in a catalytic asymmetric ring-opening reaction of meso-aziridines with TMSCN, a useful reaction for the synthesis of optically active beta-amino acids. The Gd complex generated from Gd(OiPr)3 and

  不对称多金属催化剂的新手性配体是基于通过修改模块化单元来稳定高阶组装结构的假设而设计的。设计的配体 6 和 7 包含支架环己烷环，路易斯碱氧化膦直接连接到支架上。多金属配合物中的一个模块每个配体含有两种金属，应生成稳定的 6-、5-、5-元稠合螯合环系统。这些配体的合成简单且产率高，使用由 Trost 催化剂促进的催化动态动力学拆分作为关键步骤。在内消旋氮丙啶与 TMSCN 的催化不对称开环反应中评估配体功能，这是合成光学活性 β-氨基酸的有用反应。由 Gd(OiPr)3 和配体生成的 Gd 配合物是该反应中的高活性和对映选择性催化剂。与先前报道的含有相同手性的单个模块的 d-葡萄糖衍生催化剂相比，对映选择性是相反的。ESI-MS 分析和 X 射线晶体学研究表明，多金属催化剂中模块的组装状态因手性配体而异。高阶结构的差异源于路易斯碱相对于 Gd 金属的位置的微妙变化（一个碳）。多金属配合物
• Enantioselective Desymmetrization of<i>meso</i>-Aziridines with TMSN₃or TMSCN Catalyzed by Discrete Yttrium Complexes
  作者：Bin Wu、Judith C. Gallucci、Jon R. Parquette、T. V. RajanBabu

  DOI：10.1002/anie.200804415

  日期：2009.1.26

  Y is it so? Dimeric yttrium–salen complexes (see structure; N blue, O red, Y magenta) catalyze the highly enantioselective ring‐opening of meso‐aziridines by TMSCN and TMSN3. To explain the dramatic differences in the selectivity between mono‐ and dimeric catalysts, a dimetallic mechanism based on the solid‐state structure of the dimer is proposed.

  是这样吗 钇-salen二聚体（见结构； N蓝色，O红色，Y品红色）通过TMSCN和TMSN 3催化内消旋氮丙啶的高度对映选择性开环。为了解释单聚体催化剂和二聚体催化剂之间选择性的巨大差异，提出了一种基于二聚体固态结构的双金属机理。
• Novel asymmetric ring-opening reactions of symmetrical N-acylaziridines with arenethiols catalysed by chiral dialkyl tartrate–diethylzinc complexes
  作者：Masahiko Hayashi、Kazuyuki Ono、Haruhisa Hoshimi、Nobuki Oguni

  DOI：10.1039/c39940002699

  日期：——

  The asymmetric ring-opening reaction of N-acylaziridines with arenethiols proceeds in the presence of chiral zinc complexes prepared from diethylzinc and L-(+)-diisopropyl tartrate (dipt) to afford trans-2-thio-(N-acylamino)cyclohexane in up to 88% enantiomeric excess (e.e.).

  在由二乙基锌和L -（+）-酒石酸二异丙酯（dipt）制得的手性锌配合物的存在下，N-酰基氮丙啶与芳硫醇的不对称开环反应进行，得到反式-2-硫代-（N-酰基氨基）环己烷。高达88％的对映体过量（ee）。
• Enantioselective desymmetrization of meso-aziridines with aromatic thiols catalyzed by chiral bifunctional quaternary phosphonium salts derived from α-amino acids
  作者：Jiaxing Zhang、Dongdong Cao、Hongyu Wang、Gang Zhao、Yongjia Shang

  DOI：10.1016/j.tet.2015.02.001

  日期：2015.3

  Desymmetrization of meso-aziridines with aromatic thiols was realized by using alpha-amino acids-derived chiral quaternary phosphonium salts catalysts to provide chiral beta-amino sulfides with high yields (up to 99%) and in moderate enantioselectivities (up to 70%). (C) 2015 Elsevier Ltd. All rights reserved.
• Toward a rational design of the assembly structure of polymetallic asymmetric catalysts: design, synthesis, and evaluation of new chiral ligands for catalytic asymmetric cyanation reactions
  作者：Ikuo Fujimori、Tsuyoshi Mita、Keisuke Maki、Motoo Shiro、Akihiro Sato、Sanae Furusho、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1016/j.tet.2007.02.081

  日期：2007.6

  New chiral ligands (4 and 5) for polymetallic asymmetric catalysts were designed based on the hypothesis that the assembled structure should be stable when made from a stable module 8. A metal-ligand 5:6+mu-oxo+OH complex was generated from Gd((OPr)-Pr-i)(3) and 4 or 5, and this complex was an improved asymmetric catalyst for the desymmetrization of meso-aziridines with TMSCN and conjugate addition of TMSCN to alpha,beta-unsaturated N-acylpyrroles, compared to the previously reported catalysts derived from 1-3. These two groups of catalysts produced opposing enantioselectivity even though the ligands had the same chirality. The functional difference in the asymmetric catalysts is derived from differences in the higher-order structure of the polymetallic catalysts. (C) 2007 Elsevier Ltd. All rights reserved.