Benzoic acid (2R,3R,3aR,4R,6R)-3-(dimethyl-phenyl-silanyl)-2-(S)-oxiranyl-6-((1S,2R)-2-phenyl-cyclohexyloxy)-hexahydro-isoxazolo[2,3-b][1,2]oxazin-4-yl ester | 268202-18-2

• 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 (2R,3R,3aR,4R,6R)-3-(dimethyl-phenyl-silanyl)-2-(S)-oxiranyl-6-((1S,2R)-2-phenyl-cyclohexyloxy)-hexahydro-isoxazolo[2,3-b][1,2]oxazin-4-yl ester
• 英文别名: [(2R,3R,3aR,4R,6R)-3-[dimethyl(phenyl)silyl]-2-[(2S)-oxiran-2-yl]-6-[(1S,2R)-2-phenylcyclohexyl]oxy-2,3,3a,4,5,6-hexahydro-[1,2]oxazolo[2,3-b]oxazin-4-yl] benzoate
• CAS: 268202-18-2
• 化学式: C₃₅H₄₁NO₆Si
• 分子量: 599.799
• InChiKey: PZNACBFOPLYXIP-UMQSSXSOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.99
• 重原子数：
  43
• 可旋转键数：
  9
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  69.8
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  Benzoic acid (2R,3R,3aR,4R,6R)-3-(dimethyl-phenyl-silanyl)-2-(S)-oxiranyl-6-((1S,2R)-2-phenyl-cyclohexyloxy)-hexahydro-isoxazolo[2,3-b][1,2]oxazin-4-yl ester 在 Ra-Ni 氢气 作用下， 以 甲醇 为溶剂， 以27%的产率得到(1R,2R,3R,7R,7aR)-7-(benzyloxy)-1-(dimethylphenylsilyl)hexahydro-3-hydroxymethyl-1H-pyrrolizin-2-ol
  参考文献：
  名称：

  Synthesis of (−)-7-Epiaustraline and (−)-1-Epicastanospermine

  摘要：

  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.

  DOI：

  10.1021/jo991990d
• 作为产物：
  描述：

  Benzoic acid (2R,3R,3aR,4R,6R)-3-(dimethyl-phenyl-silanyl)-2-[(S)-1-hydroxy-2-(toluene-4-sulfonyloxy)-ethyl]-6-((1S,2R)-2-phenyl-cyclohexyloxy)-hexahydro-isoxazolo[2,3-b][1,2]oxazin-4-yl ester 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 生成 Benzoic acid (2R,3R,3aR,4R,6R)-3-(dimethyl-phenyl-silanyl)-2-(S)-oxiranyl-6-((1S,2R)-2-phenyl-cyclohexyloxy)-hexahydro-isoxazolo[2,3-b][1,2]oxazin-4-yl ester
  参考文献：
  名称：

  Synthesis of (−)-7-Epiaustraline and (−)-1-Epicastanospermine

  摘要：

  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.

  DOI：

  10.1021/jo991990d

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.