7-(3,5-dinitrobenzoyl)-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-(3,5-dinitrobenzoyl)-7-azabicyclo[4.1.0]heptane
• 英文别名: N-(3,5-dinitrobenzoyl)-7-azabicyclo[4.1.0]heptane；7-azabicyclo[4.1.0]heptan-7-yl(3,5-dinitrophenyl)methanone；[(1S,6R)-7-azabicyclo[4.1.0]heptan-7-yl]-(3,5-dinitrophenyl)methanone
• 化学式: C₁₃H₁₃N₃O₅
• 分子量: 291.263
• InChiKey: KWJNKJYVTMQZAN-ONXXMXGDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  21
• 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：
  112
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  7-(3,5-dinitrobenzoyl)-7-azabicyclo[4.1.0]heptane 在 盐酸 、 (R)-VAPOL 、 苯基溴化硒 、 silver trifluoromethanesulfonate 作用下， 以 二氯甲烷 、 水 、 甲苯 为溶剂， 反应 144.0h， 生成 1S,2R-氨基环己醇盐酸盐
  参考文献：
  名称：

  A general phosphoric acid-catalyzed desymmetrization of meso-aziridines with silylated selenium nucleophiles

  摘要：

  首次报道了硒亲核试剂参与的中位氮杂环丙烷去对称化反应。该反应以VAPOL磷酸氢二钠为促进剂，采用（苯硒基）三甲基硅烷作为亲核试剂，其适用范围非常广泛，且具有高度的对映选择性（84-99% 对映体过量）。

  DOI：

  10.1039/c1ob05837a
• 作为产物：
  描述：

  2-叠氮环己基醇 在 三乙胺 、 三苯基膦 作用下， 以 乙腈 为溶剂， 反应 21.83h， 生成 7-(3,5-dinitrobenzoyl)-7-azabicyclo[4.1.0]heptane
  参考文献：
  名称：

  Phosphine-Catalyzed Heine Reaction

  摘要：

  Aziridines are important synthetic Intermediates which readily undergo ring-opening reactions. It is demonstrated that electron-rich phosphines are efficient catalysts for the regioselective rearrangement of N-acylaziridines to oxazolines. The reactions occur in excellent yield under neutral conditions. Evidence is provided for an addition/elimination mechanism by generation of a phosphonium intermediate. Similar intermediates may be useful for the development of alternate aziridine ring-opening processes and stereoselective synthesis with enantiopure phosphines.

  DOI：

  10.1021/ol202410v

文献信息

• Magnesium Complexes as Highly Effective Catalysts for Conjugate Cyanation of α,β-Unsaturated Amides and Ketones
  作者：Jinlong Zhang、Xihong Liu、Rui Wang

  DOI：10.1002/chem.201304835

  日期：2014.4.22

  Asymmetric cyanation of trimethylsilyl cyanide (TMSCN) with α,β‐unsaturated amides and ketones, respectively, catalyzed by bifunctional mononuclear 1,1′‐bi‐2‐naphthol (BINOL)–Mg and binuclear bis(prophenol)–Mg catalysts was realized. A series of synthetically important 1,4‐cyano products were obtained with good to high enantioselectivities (up to 97 % ee).

  实现了双官能单核1,1'-双-2-萘酚（BINOL）-Mg和双核双（前酚）-Mg催化剂分别催化三甲基甲硅烷基氰化物（TMSCN）与α，β-不饱和酰胺和酮的不对称氰化。获得了一系列具有重要至高对映选择性（高达97％ee）的重要的1,4-氰基合成产物 。
• Catalytic Enantioselective Ring-Opening Reaction of<i>meso</i>-Aziridines with α-Isothiocyanato Imides
  作者：Yi-Ming Cao、Fu-Ting Zhang、Fang-Fang Shen、Rui Wang

  DOI：10.1002/chem.201300297

  日期：2013.7.15

  Open up your chemistry! By using cinchonine‐based trimeric quaternary ammonium salts as catalysts, meso‐aziridines can be ring‐opened, in an enantioselective manner, through nucleophilic addition of the sulfur atom of α‐isothiocyanato imides (see scheme; PG=protecting group). This synthetic method provides an efficient way to access useful chiral β‐aminothiooxazole compounds.

  打开你的化学！通过使用基于辛可宁的三聚体季铵盐作为催化剂，可以通过亲核加成α-异硫氰酸根酰亚胺的硫原子，以对映选择性的方式将内消旋氮丙啶开环（参见方案; PG =保护基）。这种合成方法提供了一种有效的途径来获得有用的手性β-氨基硫恶唑化合物。
• 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.
• Scalable Synthesis of <i>N</i>-Acylaziridines from <i>N</i>-Tosylaziridines
  作者：Heather Rubin、Jennifer Cockrell、Jeremy B. Morgan

  DOI：10.1021/jo401267j

  日期：2013.9.6

  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.
• De Novo Synthesis of Tamiflu via a Catalytic Asymmetric Ring-Opening of <i>meso</i>-Aziridines with TMSN₃
  作者：Yuhei Fukuta、Tsuyoshi Mita、Nobuhisa Fukuda、Motomu Kanai、Masakatsu Shibasaki

  DOI：10.1021/ja061696k

  日期：2006.5.1

  An asymmetric ring-opening reaction of meso-aziridines with TMSN3 was developed using a catalyst prepared from Y(OiPr)3 and chiral ligand 2 in a 1:2 ratio. Excellent enantioselectivity was realized from a wide range of substrates with a practical catalyst loading. The products were efficiently converted to enantiomerically enriched 1,2-diamines, which are versatile chiral building blocks for pharmaceuticals and chiral ligands. This reaction was applied to a catalytic asymmetric synthesis of Tamiflu, a very important anti-influenza drug containing a chiral 1,2-diamino functionality.