ent-3-O-[(1,1-Dimethylethyl)dimethylsilyl]-(3β,17Z)-pregna-5,17(20)-dien-3-ol | 139871-19-5

• 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: ent-3-O-[(1,1-Dimethylethyl)dimethylsilyl]-(3β,17Z)-pregna-5,17(20)-dien-3-ol
• 英文别名: tert-butyl-[[(3R,8R,9R,10S,13R,14R,17Z)-17-ethylidene-10,13-dimethyl-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-3-yl]oxy]-dimethylsilane
• CAS: 139871-19-5
• 化学式: C₂₇H₄₆OSi
• 分子量: 414.747
• InChiKey: TYBHSJDWDQASHT-VIYCRCRTSA-N

物化性质

• 沸点：
  452.6±45.0 °C(Predicted)
• 密度：
  0.97±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.29
• 重原子数：
  29
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  ent-3-O-[(1,1-Dimethylethyl)dimethylsilyl]-(3β,17Z)-pregna-5,17(20)-dien-3-ol 在 platinum on activated charcoal 吡啶 、 四丁基氟化铵 、 氢气 、 氯化二乙基铝 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 乙醚 、 乙醇 、 二氯甲烷 为溶剂， 反应 6.0h， 生成 ent-cholesterol
  参考文献：
  名称：

  A new method for the preparation of ent-cholesterol from ent-testosterone

  摘要：

  An efficient total synthesis of the enantiomer of cholesterol is reported. The enantiomer of testosterone was prepared and converted into a C-21 3-silyloxy-Delta(5,17(20))-diene according to literature procedures. The additional five carbon atoms of the cholesterol side chain were introduced by an ene reaction. Selective hydrogenation of the resultant Delta(16) double bond and removal of the 22-hydroxyl group by a mesylation and demesylation sequence gave ent-cholesterol in 9.7% overall yield from ent-testosterone (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(98)02588-x
• 作为产物：
  描述：

  (-)-3β-tert-Butoxy-3aβ-methyl-1,1,3,3a,4,5,8,9,9aβ,9bα-decahydro-6-<2-(2-methyl-1,3-dioxolan-2-yl)ethyl>-7H-benzinden-7-one 在 盐酸 、 4-二甲氨基吡啶 、 4 A molecular sieve 、 potassium tert-butylate 、 氨 、 lithium 、 lithium tri-t-butoxyaluminum hydride 、 三乙胺 、 pyridinium chlorochromate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 叔丁醇 为溶剂， 反应 56.75h， 生成 ent-3-O-[(1,1-Dimethylethyl)dimethylsilyl]-(3β,17Z)-pregna-5,17(20)-dien-3-ol
  参考文献：
  名称：

  Synthesis of ent-cholesterol, the unnatural enantiomer

  摘要：

  Cholesterol is ubiquitious in mammals and plays an important role in human health. The unique relationship between enantiomers makes ent-cholesterol, the unnatural enantiomer of cholesterol, a valuable new probe of cholesterol function in biochemical systems. We report the first enantioselective total synthesis of ent-cholesterol.

  DOI：

  10.1021/jo00035a036

文献信息

• Neurosteroid Analogues. 6. The Synthesis and GABA_A Receptor Pharmacology of Enantiomers of Dehydroepiandrosterone Sulfate, Pregnenolone Sulfate, and (3α,5β)-3-Hydroxypregnan-20-one Sulfate
  作者：Kent R. Nilsson、Charles F. Zorumski、Douglas F. Covey

  DOI：10.1021/jm980148h

  日期：1998.7.1

  The unnatural enantiomers of dehydroepiandrosterone sulfate (1), pregnenolone sulfate (2), and (3 alpha,5 beta)-3-hydroxypregnan-20-one sulfate (3), compounds 4-6, respectively, were prepared by total steroid synthesis. The enantioselectivity of the compounds as negative modulators of the GABA(A) receptors present in cultured rat hippocampal neurons was examined using electrophysiological methods. Enantioselectivity was found for the inhibitory actions of the dehydroepiandrosterone enantiomers, The IC(50)s for compounds 1 and 4 were 11 +/- 1 and 80 +/- 14 mu M, respectively. Little, if any, enantioselectivity was found for the other two pairs of steroid sulfate inhibitors. The IC(50)s for compounds 2 and 5 were 82 +/- 12 and 76 +/- 27 mu M, respectively. The IC(50)s for compounds 3 and 6 were 39 +/- 7 and 46 +/- 2 mu M, respectively. The results suggest that the sites of action for the androstane and pregnane series of steroid sulfate blockers of GABA-mediated current are different. The observed enantioselectivity for the actions of dehydroepiandrosterone sulfate indicates that its inhibitory actions are mediated via a chiral recognition site and provides new evidence in support of the earlier hypothesis that there is a binding site for this compound on GABA(A) receptors. Conversely, the failure to observe enantioselectivity for the actions of pregnenolone sulfate and steroid sulfate 3 indicates that a chiral recognition site far these steroids does not exist on GABA(A) receptors and suggests that the effects of these compounds on this receptor's function may arise indirectly as a consequence of steroid-induced membrane perturbation.
• A new method for the preparation of ent-cholesterol from ent-testosterone
  作者：A.Sampath Kumar、Douglas F. Covey

  DOI：10.1016/s0040-4039(98)02588-x

  日期：1999.1

  An efficient total synthesis of the enantiomer of cholesterol is reported. The enantiomer of testosterone was prepared and converted into a C-21 3-silyloxy-Delta(5,17(20))-diene according to literature procedures. The additional five carbon atoms of the cholesterol side chain were introduced by an ene reaction. Selective hydrogenation of the resultant Delta(16) double bond and removal of the 22-hydroxyl group by a mesylation and demesylation sequence gave ent-cholesterol in 9.7% overall yield from ent-testosterone (C) 1999 Elsevier Science Ltd. All rights reserved.
• Synthesis of ent-cholesterol, the unnatural enantiomer
  作者：Scott D. Rychnovsky、Daniel E. Mickus

  DOI：10.1021/jo00035a036

  日期：1992.4

  Cholesterol is ubiquitious in mammals and plays an important role in human health. The unique relationship between enantiomers makes ent-cholesterol, the unnatural enantiomer of cholesterol, a valuable new probe of cholesterol function in biochemical systems. We report the first enantioselective total synthesis of ent-cholesterol.