4-hydroxy-4-(pivaloxymethyl)-6-(2-methoxyethoxymethyl)-6-azabicyclo[3.1.0]hex-2-ene

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 4-hydroxy-4-(pivaloxymethyl)-6-(2-methoxyethoxymethyl)-6-azabicyclo[3.1.0]hex-2-ene
• 英文别名: [(1R,2R,5R)-2-hydroxy-6-(2-methoxyethoxymethyl)-6-azabicyclo[3.1.0]hex-3-en-2-yl]methyl 2,2-dimethylpropanoate
• 化学式: C₁₅H₂₅NO₅
• 分子量: 299.367
• InChiKey: KCEYNXMNWMKSPI-ZXJTVVTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  21
• 可旋转键数：
  9
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  68
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 4-hydroxy-4-(pivaloxymethyl)-6-(2-methoxyethoxymethyl)-6-azabicyclo[3.1.0]hex-2-ene 在 溶剂黄146 、 盐酸 、 吡啶 、 4-二甲氨基吡啶 作用下， 以 甲醇 为溶剂， 反应 29.0h， 以80%的产率得到(-)-3,5-diacetoxy-4-N-acetylamino-5-(pivaloxymethyl)cyclopent-1-ene
  参考文献：
  名称：

  Pyridinium Salt Photochemistry in a Concise Route for Synthesis of the Trehazolin Aminocyclitol, Trehazolamine

  摘要：

  A strategy for the concise synthesis of trehazolamine, the aminocyclitol core of the potent trehalase inhibitor trehazolin, has been developed. The methodology takes advantage of photocyclization reaction of 1-methoxyethoxymethyl-3-pivaloxymethylpyridinium perchlorate to generate a bicyclicaziridine intermediate, which is transformed under aziridine ring opening conditions to the key intermediate, 3,5-diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentene. In addition, the strategy is used in an enantio-divergent sequence for preparation of the natural (+)-trehazolamine and its unnatural (-)-enantiomer. In this route, the chiral auxiliary containing 1-(tetracetyl-alpha-D-glucosyl)-3-pivaloxymethylpyridinium perchlorate undergoes photocyclization to generate separable, diastereomeric bicyclic-aziridines, which are then independently transformed to enantiomeric 3,5diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentenes.

  DOI：

  10.1021/jo050589q
• 作为产物：
  描述：

  3-吡啶甲醇 在 TEA 、 碳酸氢钠 作用下， 以 水 、 乙酸乙酯 、 乙腈 为溶剂， 反应 6.33h， 生成 4-hydroxy-4-(pivaloxymethyl)-6-(2-methoxyethoxymethyl)-6-azabicyclo[3.1.0]hex-2-ene
  参考文献：
  名称：

  Pyridinium Salt Photochemistry in a Concise Route for Synthesis of the Trehazolin Aminocyclitol, Trehazolamine

  摘要：

  A strategy for the concise synthesis of trehazolamine, the aminocyclitol core of the potent trehalase inhibitor trehazolin, has been developed. The methodology takes advantage of photocyclization reaction of 1-methoxyethoxymethyl-3-pivaloxymethylpyridinium perchlorate to generate a bicyclicaziridine intermediate, which is transformed under aziridine ring opening conditions to the key intermediate, 3,5-diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentene. In addition, the strategy is used in an enantio-divergent sequence for preparation of the natural (+)-trehazolamine and its unnatural (-)-enantiomer. In this route, the chiral auxiliary containing 1-(tetracetyl-alpha-D-glucosyl)-3-pivaloxymethylpyridinium perchlorate undergoes photocyclization to generate separable, diastereomeric bicyclic-aziridines, which are then independently transformed to enantiomeric 3,5diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentenes.

  DOI：

  10.1021/jo050589q

文献信息

• Pyridinium Salt Photochemistry in a Concise Route for Synthesis of the Trehazolin Aminocyclitol, Trehazolamine
  作者：Xiaohua Feng、Eileen N. Duesler、Patrick S. Mariano

  DOI：10.1021/jo050589q

  日期：2005.7.1

  A strategy for the concise synthesis of trehazolamine, the aminocyclitol core of the potent trehalase inhibitor trehazolin, has been developed. The methodology takes advantage of photocyclization reaction of 1-methoxyethoxymethyl-3-pivaloxymethylpyridinium perchlorate to generate a bicyclicaziridine intermediate, which is transformed under aziridine ring opening conditions to the key intermediate, 3,5-diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentene. In addition, the strategy is used in an enantio-divergent sequence for preparation of the natural (+)-trehazolamine and its unnatural (-)-enantiomer. In this route, the chiral auxiliary containing 1-(tetracetyl-alpha-D-glucosyl)-3-pivaloxymethylpyridinium perchlorate undergoes photocyclization to generate separable, diastereomeric bicyclic-aziridines, which are then independently transformed to enantiomeric 3,5diacetoxy-3-pivaloxymethyl-4-(N-acetylamino)cyclopentenes.