17β-O-(tetrahydropyranyl)androst-5-ene-3β,17β,19-triol | 135598-58-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 类固醇和类固醇衍生物
• 英文名称: 17β-O-(tetrahydropyranyl)androst-5-ene-3β,17β,19-triol
• CAS: 135598-58-2
• 化学式: C₂₄H₃₈O₄
• 分子量: 390.563
• InChiKey: QFGDWINBZPRERW-QMSRAGSTSA-N

物化性质

• 沸点：
  540.9±50.0 °C(Predicted)
• 密度：
  1.17±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.19
• 重原子数：
  28.0
• 可旋转键数：
  3.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  58.92
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  17β-O-(tetrahydropyranyl)androst-5-ene-3β,17β,19-triol 在 2,3,5-三甲基吡啶 、 Collins oxidation agent 、 1,5-二氮杂双环[4.3.0]壬-5-烯 、 双氧水 、 碳酸氢钠 作用下， 以 甲醇 、 二氯甲烷 、 苯 为溶剂， 反应 1.5h， 生成 3-O-(tert-butyldimethylsilyl)-17β-O'-(tetrahydropyranyl)estradiol
  参考文献：
  名称：

  Mechanistic studies on a placental aromatase model reaction

  摘要：

  Aromatase is a cytochrome P-450 enzyme that converts androgens to estrogens via three successive oxidative reactions. The mechanism of the third step has previously been intensively studied, with no clear resolution. A leading theory for the third step proposes nucleophilic attack of the heme ferric peroxide species on the 19-aldehyde intermediate to produce a 19-hydroxy 19-ferric peroxide intermediate. We have shown previously that analogues of this intermediate failed to aromatize under nonenzymatic conditions. In this study, we prepared a 2,4-dien-3-ol analogue of the 19-aldehyde intermediate and showed that it reacted with HOOH to produce the corresponding estrogen derivative. Evidence has been accrued to suggest that this reaction, which we have called the aromatase model reaction, involves a 19-hydroxy 19-hydroperoxide intermediate. The model reaction was shown to be faithful to the actual aromatase-catalyzed reaction with regard to stoichiometric formic acid production, O-18-incorporation patterns, and stereoselectivity for 1-beta-hydrogen removal. A kinetic analysis at 37-degrees-C was also performed, and the reaction was demonstrated to be pseudo-first-order by using an excess of HOOH, and first-order with respect to HOOH at the concentrations studied. The effects of KOH, EDTA, and BHT on the reaction were also examined, and are discussed.

  DOI：

  10.1021/ja00021a044
• 作为产物：
  描述：

  3β,19-dihydroxy-5-androsten-17-one 在 吡啶 、 4-二甲氨基吡啶 、 氢氧化钾 、 sodium tetrahydroborate 、 4-甲基苯磺酸吡啶 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醇 为溶剂， 反应 26.75h， 生成 17β-O-(tetrahydropyranyl)androst-5-ene-3β,17β,19-triol
  参考文献：
  名称：

  Mechanistic studies on a placental aromatase model reaction

  摘要：

  Aromatase is a cytochrome P-450 enzyme that converts androgens to estrogens via three successive oxidative reactions. The mechanism of the third step has previously been intensively studied, with no clear resolution. A leading theory for the third step proposes nucleophilic attack of the heme ferric peroxide species on the 19-aldehyde intermediate to produce a 19-hydroxy 19-ferric peroxide intermediate. We have shown previously that analogues of this intermediate failed to aromatize under nonenzymatic conditions. In this study, we prepared a 2,4-dien-3-ol analogue of the 19-aldehyde intermediate and showed that it reacted with HOOH to produce the corresponding estrogen derivative. Evidence has been accrued to suggest that this reaction, which we have called the aromatase model reaction, involves a 19-hydroxy 19-hydroperoxide intermediate. The model reaction was shown to be faithful to the actual aromatase-catalyzed reaction with regard to stoichiometric formic acid production, O-18-incorporation patterns, and stereoselectivity for 1-beta-hydrogen removal. A kinetic analysis at 37-degrees-C was also performed, and the reaction was demonstrated to be pseudo-first-order by using an excess of HOOH, and first-order with respect to HOOH at the concentrations studied. The effects of KOH, EDTA, and BHT on the reaction were also examined, and are discussed.

  DOI：

  10.1021/ja00021a044