Benzoic acid (4R,6R)-2-oxy-6-((1S,2R)-2-phenyl-cyclohexyloxy)-5,6-dihydro-4H-[1,2]oxazin-4-yl ester | 158250-17-0

• 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: Benzoic acid (4R,6R)-2-oxy-6-((1S,2R)-2-phenyl-cyclohexyloxy)-5,6-dihydro-4H-[1,2]oxazin-4-yl ester
• 英文别名: [(4R,6R)-2-oxido-6-[(1S,2R)-2-phenylcyclohexyl]oxy-5,6-dihydro-4H-oxazin-2-ium-4-yl] benzoate
• CAS: 158250-17-0
• 化学式: C₂₃H₂₅NO₅
• 分子量: 395.455
• InChiKey: LWHSQTYFQUIBQS-YUMYIRISSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.39
• 拓扑面积：
  73.5
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  马来酸二甲酯 、 Benzoic acid (4R,6R)-2-oxy-6-((1S,2R)-2-phenyl-cyclohexyloxy)-5,6-dihydro-4H-[1,2]oxazin-4-yl ester 以 苯 为溶剂， 反应 10.5h， 以88%的产率得到(-)-(2S,3aS,3R,4R,6R)-3-Carbomethoxy-4-(benzoyloxy)-6-<(1S,2R)-2-phenyl-cyclohexyloxy>hexahydroisoxazolo<1,7-b> <1,2>oxazine-2-carboxylic acid methyl ester
  参考文献：
  名称：

  The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine

  摘要：

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.

  DOI：

  10.1021/jo00098a027
• 作为产物：
  描述：

  苯甲酰氯 、 alkaline earth salt of/the/ methylsulfuric acid 在 二异丙氧基二氯化钛 作用下， 以 硝基甲烷 、 二氯甲烷 为溶剂， 反应 6.92h， 生成 Benzoic acid (4R,6R)-2-oxy-6-((1S,2R)-2-phenyl-cyclohexyloxy)-5,6-dihydro-4H-[1,2]oxazin-4-yl ester
  参考文献：
  名称：

  The Tandem Cycloaddition Chemistry of Nitroalkenes. A Novel Synthesis of (-)-Hastanecine

  摘要：

  A short and efficient asymmetric synthesis of the pyrrolizidine necine base (-)-hastanecine is described. The key reaction in the synthesis is a sequential inter [4+2]/inter[3+2] cycloaddition. The Lewis acid promoted [4+2] cycloaddition between 2-acyloxy nitroalkene 16 and chiral vinyl ether 17 afforded a nitronate which underwent facile [3+2] cycloaddition with dimethyl maleate. The resulting nitroso acetal 19 had all the required stereocenters for (-)-hastanecine. The critical unmasking of the nitroso acetal 19 employed a hydrogenolytic cleavage to give the 1-azabicyclo-[3.3.0]octane skeleton of (-)-hastanecine.

  DOI：

  10.1021/jo00098a027

文献信息

• Synthesis of (−)-7-Epiaustraline and (−)-1-Epicastanospermine
  作者：Scott E. Denmark、B. Herbert

  DOI：10.1021/jo991990d

  日期：2000.5.1

  Highly efficient and selective syntheses of the title compounds are described. The cornerstone of the synthetic plan is the tandem inter [4 + 2]/inter [3 + 2] cycloaddition process. These syntheses differ from previous applications of this strategy in that they incorporate an alkylation in the hydrogenolysis step to close the second ring of the azabicyclic systems. Notable features of the sequence are (1) the highly regio- and stereoselective [3 + 2] cycloaddition of nitronate 15 with siloxymethyl (Z)-beta-silylvinyl ketone (Z)-22b and (2) the highly selective reduction of the resulting ketone 24a with L-Selectride. A single-crystal X-ray structure analysis of synthetic (-)-7-epiaustraline confirmed that the targeted structure was successfully synthesized. This stimulated a reexamination of the structural assignment of the natural product. (-)-1-Epicastanospermine was synthesized in four steps from the common intermediate 27a. The absolute configuration of (-)-1-epicastanospermine was assured by single-crystal X-ray structure analysis of intermediate (-)-27a. Thus, the sign of the optical rotation had to be revised. The overall efficiency of these syntheses were 9 steps and 23% yield for (-)-7-epiaustraline and 10 steps and 20% yield for (-)-1-epicastanospermine.
• Synthesis of (1<i>R</i>,2<i>R</i>,3<i>R</i>,7<i>R</i>,7a<i>R</i>)-Hexahydro-3-(Hydroxymethyl)-1<i>H</i>-pyrrolizine-1,2,7-triol:  7-Epiaustraline
  作者：Scott E. Denmark、B. Herbert

  DOI：10.1021/ja980705p

  日期：1998.7.1