(1S,2S)-1-cyano-2-[N-(4-nitrobenzoyl)amino]cyclohexane | 864445-67-0

• 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: (1S,2S)-1-cyano-2-[N-(4-nitrobenzoyl)amino]cyclohexane
• 英文别名: N-[(1S,2S)-2-cyanocyclohexyl]-4-nitrobenzamide
• CAS: 864445-67-0
• 化学式: C₁₄H₁₅N₃O₃
• 分子量: 273.291
• InChiKey: GEEAGGACYFJNIX-YPMHNXCESA-N

物化性质

• 沸点：
  535.7±45.0 °C(Predicted)
• 密度：
  1.27±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  98.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1S,2S)-1-cyano-2-[N-(4-nitrobenzoyl)amino]cyclohexane 在 盐酸 作用下， 反应 120.0h， 以92%的产率得到(1S,2S)-2-氨基环己甲酸
  参考文献：
  名称：

  Catalytic Enantioselective Desymmetrization of meso-N-Acylaziridines with TMSCN

  摘要：

  A catalytic enantioselective desymmetrization of meso-N-p-nitrobenzoylaziridines with TMSCN was developed using a chiral gadolinium catalyst generated from Gd(OiPr)3 and d-glucose-derived ligand 1. In this reaction, the addition of a catalytic amount of trifluoroacetic acid (TFA) improved enantioselectivity. High enantioselectivity was obtained from a range of meso-aziridines at 0-60 degrees C. The product could be easily transformed into beta-amino acids. Thus, the developed catalytic enantioselective desymmetrization reaction allowed for efficient catalytic synthesis of chiral cyclic beta-amino acids. The incorporation of TFA into the catalyst complex was observed using ESI-MS. Generation of this new complex might be the origin of the improved enantioselectivity.

  DOI：

  10.1021/ja053486y
• 作为产物：
  描述：

  7-(4-nitrobenzoyl)-7-azabicyclo[4.1.0]heptane 、 三甲基氰硅烷 在 (1R,2R,6S)-6-diphenylphosphinylmethyl-2-(4',5'-difluoro-2'-phenoxy)cyclohexanol 、 gadolinium(III) isopropoxide 2,6-二甲基苯酚 、 三氟乙酸 作用下， 以 丙腈 为溶剂， 反应 20.0h， 以94%的产率得到(1S,2S)-1-cyano-2-[N-(4-nitrobenzoyl)amino]cyclohexane
  参考文献：
  名称：

  EP1995250

  摘要：

  公开号：

文献信息

• Bimetallic catalysis in the highly enantioselective ring–opening reactions of aziridines
  作者：Bin Wu、Judith C. Gallucci、Jon R. Parquette、T. V. RajanBabu

  DOI：10.1039/c3sc52929k

  日期：——

  lanthanide-salen complexes, readily prepared from commercially available metal isopropoxides, 2-dimethylaminoethanol, 1,1′-binaphthyl-2,2′-diamine and 2-hydroxy-3-methoxybenzaldehyde (3 steps) catalyze highly enantioselective ring opening (∼90–99% ee) reactions of meso-N-4-nitrobenzoyl aziridines by TMSCN and TMSN3. The TMSN3-mediated reactions give the highest enantioselectivities reported to date

  由市售金属异丙醇，2-二甲基氨基乙醇，1,1'-萘基-2,2'-二胺和2-羟基-3-甲氧基苯甲醛容易制得的双金属钇-镧系元素-salen配合物（3个步骤）催化高对映选择性TMSCN和TMSN 3引发中-N -4-硝基苯甲酰基氮丙啶类化合物的开环反应（〜90-99％ee）3。迄今为止，对于几种原型氮丙啶，TMSN 3介导的反应具有最高的对映选择性。异硫氰酸甲硅烷基酯在相关开环中的选择性取决于硅上的取代基，t BuPh 2较大SiNCS具有最佳选择性，尤其是在使用钇或配合物作为催化剂时。与TMSN 3反应后，双金属钇配合物还影响外消旋单取代氮丙啶的前所未有的区域发散平行动力学拆分。在这些反应中，每种对映异构体在不同的碳原子上进行叠氮化物的亲核加成，从而得到两种对映体纯的形式。为了解释这些反应中单金属催化剂和双金属催化剂之间选择性的显着差异，提出了一种机制，涉及在双金属络合物的两种不同金属上亲电
• 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。
• 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.
• Catalytic Enantioselective Desymmetrization of <i>meso</i>-<i>N</i>-Acylaziridines with TMSCN
  作者：Tsuyoshi Mita、Ikuo Fujimori、Reiko Wada、Jianfeng Wen、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja053486y

  日期：2005.8.1

  A catalytic enantioselective desymmetrization of meso-N-p-nitrobenzoylaziridines with TMSCN was developed using a chiral gadolinium catalyst generated from Gd(OiPr)3 and d-glucose-derived ligand 1. In this reaction, the addition of a catalytic amount of trifluoroacetic acid (TFA) improved enantioselectivity. High enantioselectivity was obtained from a range of meso-aziridines at 0-60 degrees C. The product could be easily transformed into beta-amino acids. Thus, the developed catalytic enantioselective desymmetrization reaction allowed for efficient catalytic synthesis of chiral cyclic beta-amino acids. The incorporation of TFA into the catalyst complex was observed using ESI-MS. Generation of this new complex might be the origin of the improved enantioselectivity.
• EP1995250
  申请人：——

  公开号：——

  公开（公告）日：——