(2R,3R,3aR,4R,6R)-4-benzyloxy-2-{(1S)-1-hydroxy-2-[dimethyl(1,1,2-trimethylpropyl)siloxy]ethyl}-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]hexahydroisoxazolo-[1,7b][1,2]oxazine | 212612-92-5

• 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: (2R,3R,3aR,4R,6R)-4-benzyloxy-2-{(1S)-1-hydroxy-2-[dimethyl(1,1,2-trimethylpropyl)siloxy]ethyl}-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]hexahydroisoxazolo-[1,7b][1,2]oxazine
• 英文别名: [(2R,3R,3aR,4R,6R)-2-[(1S)-2-[2,3-dimethylbutan-2-yl(dimethyl)silyl]oxy-1-hydroxyethyl]-3-[dimethyl(phenyl)silyl]-6-[(1S,2R)-2-phenylcyclohexyl]oxy-2,3,3a,4,5,6-hexahydro-[1,2]oxazolo[2,3-b]oxazin-4-yl] benzoate
• CAS: 212612-92-5
• 化学式: C₄₃H₆₁NO₇Si₂
• 分子量: 760.131
• InChiKey: KFDJYHPMYLLYQJ-DGAUCCEKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.61
• 重原子数：
  53.0
• 可旋转键数：
  13.0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  86.69
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (2R,3R,3aR,4R,6R)-4-benzyloxy-2-{(1S)-1-hydroxy-2-[dimethyl(1,1,2-trimethylpropyl)siloxy]ethyl}-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]hexahydroisoxazolo-[1,7b][1,2]oxazine 、 甲基磺酸酐 在 吡啶 作用下， 以96%的产率得到(2R,3R,3aR,4R,6R)-4-benzyloxy-2-{(1S)-2-[dimethyl(1,1,2-trimethylpropyl)siloxy]-1-[(methanesulfonyl)oxy]ethyl}-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]hexahydroisoxazolo-[1,7b][1,2]oxazine
  参考文献：
  名称：

  Synthesis of (1R,2R,3R,7R,7aR)-Hexahydro-3-(Hydroxymethyl)-1H-pyrrolizine-1,2,7-triol:  7-Epiaustraline

  摘要：

  DOI：

  10.1021/ja980705p
• 作为产物：
  描述：

  (Z)-1,4-bis-(dimethyl(1,1,2-trimethylpropyl)silyloxy)-2-butene 在 光气 、 bis(cyclohexanyl)borane 、 乙基溴化镁 、 L-Selectride 、 臭氧 、 二甲基亚砜 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 18.83h， 生成 (2R,3R,3aR,4R,6R)-4-benzyloxy-2-{(1S)-1-hydroxy-2-[dimethyl(1,1,2-trimethylpropyl)siloxy]ethyl}-3-(dimethylphenylsilyl)-6-[(1S,2R)-(2-phenylcyclohexyl)oxy]hexahydroisoxazolo-[1,7b][1,2]oxazine
  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