(+/-)-exo-8-Methyl-2,4-dioxo-3-(phenylmethyl)-3,8-diazabicyclo<3.2.1>octane-6-carboxylic acid methyl ester | 120566-63-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 哌啶类
• 英文名称: (+/-)-exo-8-Methyl-2,4-dioxo-3-(phenylmethyl)-3,8-diazabicyclo<3.2.1>octane-6-carboxylic acid methyl ester
• 英文别名: methyl (1S,5R,6R)-3-benzyl-8-methyl-2,4-dioxo-3,8-diazabicyclo[3.2.1]octane-6-carboxylate
• CAS: 120566-63-4
• 化学式: C₁₆H₁₈N₂O₄
• 分子量: 302.33
• InChiKey: LGDBOXCYTCJHTC-FRRDWIJNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.42
• 重原子数：
  22.0
• 可旋转键数：
  3.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  66.92
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  6-Methyl-3-(phenylmethyl)-3,6-diazabicyclo<3.1.0>hexane-2,4-dione 、 丙烯酸甲酯（MA） 以 1,4-二氧六环 为溶剂， 反应 10.0h， 以50%的产率得到(+/-)-exo-8-Methyl-2,4-dioxo-3-(phenylmethyl)-3,8-diazabicyclo<3.2.1>octane-6-carboxylic acid methyl ester
  参考文献：
  名称：

  Development of an asymmetric approach to the 3,8-diazabicyclo[3.2.1]octane moiety of quinocarcin via intramolecular 1,3-dipolar cycloadditions of photochemically generated azomethine ylides

  摘要：

  Exploratory work culminating in an enantioselective approach to the DNA-reactive alkaloid quinocarcin (1) is detailed. The key step involves auxiliary-controlled dipolar cycloaddition between photochemically generated azomethine ylides such as 11 and Oppolzer's chiral acryloyl sultam (-)-32 to assemble the 6-exo-substituted 3,8-diazabicyclo[3.2.1]octane core of 1. The synthetic sequence begins with condensation of the benzylamines 3 and maleic anhydride to give the N-alkylated maleimides 6. Triazoline formation (MeN3) followed by photolytic (lambda > 3000 angstrom) extrusion of nitrogen leads to the corresponding aziridines 10. Upon irradiation at 2537 angstrom, these aziridines undergo electrocyclic ring-opening to give azomethine ylides 11, which can be trapped with (-)-32 to give the 6-exo-substituted cycloadduct 33 (diastereoselectivity, ds > 25:1). These results stand in sharp contrast to cycloadditions of 11 with (achiral and chiral) acrylate ester dipolarophiles as well as acrylonitrile, which proceed with no appreciable facial selectivity. The expected re-face selectivity of (-)-32 was confirmed in one case by X-ray crystallographic analysis of endo-adduct 35a. Removal (and recovery) of the chiral sultam auxiliary can be effected by titanium (IV)-mediated alcoholysis to give ester derivatives of the cycloadducts.

  DOI：

  10.1021/jo00020a035

文献信息

• An approach to the 3,8-diazabicyclo[3.2.1]octane moiety of naphthyridinomycin and quinocarcin via 1,3-dipolar cycloaddition of photochemically generated azomethine ylides.
  作者：Philip Garner、K. Sunitha、T. Shanthilal

  DOI：10.1016/0040-4039(88)85283-3

  日期：1988.1

  An attractive strategy for construction of the 3,8-diazabicyclo[3.2.1]octane moiety of targets 1 and 2 involving the 1,3-dipolar cycloaddition of photochemically generated azomethine ylides is presented.

  提出了一种有吸引力的策略，用于构建目标1和2的3,8-二氮杂双环[3.2.1]辛烷部分，涉及光化学生成的甲亚胺基团的1,3-偶极环加成。