11α-hydroxy-5α-androstan-3,17-dione | 29907-31-1

• 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: 11α-hydroxy-5α-androstan-3,17-dione
• 英文别名: 11alpha-Hydroxy-5alpha-androstane-3,17-dione；(5S,8S,9S,10S,11R,13S,14S)-11-hydroxy-10,13-dimethyl-2,4,5,6,7,8,9,11,12,14,15,16-dodecahydro-1H-cyclopenta[a]phenanthrene-3,17-dione
• CAS: 29907-31-1
• 化学式: C₁₉H₂₈O₃
• 分子量: 304.43
• InChiKey: FZEAQJIXYCPBLD-ZEEXRJDKSA-N

物化性质

• 熔点：
  178-180 °C(Solv: dichloromethane (75-09-2); ethyl ether (60-29-7))
• 沸点：
  453.4±45.0 °C(Predicted)
• 密度：
  1.152±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.89
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  11α-hydroxy-5α-androstan-3,17-dione 在 吡啶 、 三氯氧磷 作用下， 反应 18.0h， 以70%的产率得到(5α)-androst-9(11)-ene-3,17-dione
  参考文献：
  名称：

  Crabb, Trevor A.; Ratcliffe, Norman M., Journal of Chemical Research, Miniprint, 1986, # 2, p. 650 - 669

  摘要：

  DOI：
• 作为产物：
  描述：

  5a-雄甾烷二酮 以 乙醇 为溶剂， 反应 72.0h， 以66%的产率得到11α-hydroxy-5α-androstan-3,17-dione
  参考文献：
  名称：

  Crabb, Trevor A.; Ratcliffe, Norman M., Journal of Chemical Research, Miniprint, 1986, # 2, p. 650 - 669

  摘要：

  DOI：

文献信息

• Water Soluble Steroids with Catalytic Substituents II. Synthesis of 3β-(4(5)-Imidazolyl)-5α-androstane-11β, 17β,-diamine and Comparison of its Catalytic Properties with Those of 17β-(4(5)-Imidazolyl)-5α-androstane-3β, 11β-diamine
  作者：J. Peter Guthrie、Yasutsugu Ueda

  DOI：10.1139/v73-586

  日期：1973.12.1

  3β-(4(5)-Imidazolyl)-5α-androstane-11β,17β-diamine, 15, has been synthesized in a multistep process from adrenosterone, 2, starting with lithium ammonia reduction to give 11α,17β-dihydroxy-5α-androstan-3-one, 3, which was converted to its diacetate, 4. Ethynylation at the 3 keto group gave the ethynyl triol 5, purified as its11,17-diacetate 6. Acid catalyzed rearrangement of 6 gave 3-acetyl-5α-androst-2-ene-11α,17β-diol diacetate, 7. This was hydrogenated, and then subjected to base catalyzed hydrolysis and equilibration to give crystalline 3β-acetyl-5α-androstane-11α,17β-diol, 9, which was converted to 3β-acetoxyacetyl-5α-androstane-11α,17β-diol, 10, using lead tetraacetate. After hydrolysis to the triol, 11, the Weidenhagen reaction led to formation of 3β-imidazolyl-5α-androstane-11α,17β-diol, 12. Finally oxidation to the dione, 13, formation of the dioxime, 14, and hydrogénation give 15. As expected 15 is a better catalyst than 17β-(4(5)-imidazolyl-5α-androstane-3β,11β-diamine, 1, for the hydrolysis of aryl esters of acids with hydrophobic substituents, but the effect is small. With 1 there is a marked electrostatic rate enhancement or retardation when charged groups are present on the aryl esters; this effect is much smaller for 15.

  3β-(4(5)-咪唑基)-5α-雄烷-11β,17β-二胺，15，是从腺酮，2，经过多步合成的，首先进行锂氨还原得到11α,17β-二羟基-5α-雄甾-3-酮，3，然后转化为其二乙酸酯，4。在3酮基上进行乙炔基化得到乙炔三醇5，纯化为其11,17-二乙酸酯6。酸催化6的重排得到3-乙酰基-5α-雄烷-2-烯-11α,17β-二醇二乙酸酯，7。这经过氢化，然后经过碱催化水解和平衡得到结晶的3β-乙酰基-5α-雄烷-11α,17β-二醇，9，它被转化为3β-乙酰氧乙酰-5α-雄烷-11α,17β-二醇，10，使用四乙酸铅。水解为三醇后，11，魏登哈根反应导致形成3β-咪唑基-5α-雄烷-11α,17β-二醇，12。最后氧化为二酮，13，形成二肟，14，和氢化得到15。如预期的那样，15比17β-(4(5)-咪唑基-5α-雄烷-3β,11β-二胺，1，更好地催化含疏水取代基的芳基酯的水解，但效果很小。对于1，当芳基酯上存在带电基团时，会出现明显的静电速率增强或减缓；而对于15，这种效应要小得多。
• The hydroxylation of some 13α-methylsteroids by Cephalosporium aphidicola
  作者：Juliette Boynton、James R. Hanson、A.Christy Hunter

  DOI：10.1016/s0031-9422(97)00103-9

  日期：1997.7

  and C-7α positions, whereas the corresponding compounds in the normal 13β-methyl series are hydroxylated at the C-11α and C-14α positions. Both series were hydroxylated at the 5α-position. There was some epimerization of the axial 3α-alcohols to the equatorial 3β-epimers. © 1997 Elsevier Science Ltd. All rights reserved

  摘要 真菌 Cephalosporium aphidicola 已显示羟基化 5α,13α-androstan-3,17-dione 和 C-1α 和 C-7α 位置的 3β-醇，而正常 13β-甲基系列中的相应化合物在 C-11α 和 C-14α 位被羟基化。两个系列均在 5α 位被羟基化。轴向 3α-醇与赤道 3β-差向异构体发生了一些差向异构化。© 1997 Elsevier Science Ltd. 版权所有
• Microbial hydroxylation of epiandrosterone by <i>Aspergillus candidus</i>
  作者：Kudret Yildirim、Ali Kuru

  DOI：10.1080/10242422.2017.1289184

  日期：2017.3.4

  work, Aspergillus candidus MRC 22634 converted epiandosterone 1 into 10 hydroxylated metabolites. A. candidus has been shown to hydroxylate 1 predominantly at C-11α, C-1α, and C-15β with minor hydroxylations occurring at C-14α and C-7α. Oxidation at C-3, reduction at C-17, and C-3 epimerization of some of the remaining substrate have also been shown. 15β-Hydroxylation and C-3 epimerization of 1 by

  摘要 在这项工作中，念珠菌 MRC 22634 将表雄酮 1 转化为 10 种羟基化代谢物。A. candidus 已显示主要在 C-11α、C-1α 和 C-15β 处羟基化 1，在 C-14α 和 C-7α 处发生少量羟基化。还显示了 C-3 处的氧化、C-17 处的还原和一些剩余底物的 C-3 差向异构化。首次报道了真菌对 1 的 15β-羟基化和 C-3 差向异构化。其中两种代谢物 1α,3α-dihydroxy-5α-androstan-17-one 4 和 15β,17β-dihydroxy-5α-androstan-3-one 7 被鉴定为新化合物。
• Hydroxylation of DHEA and its analogues by Absidia coerulea AM93. Can an inducible microbial hydroxylase catalyze 7α- and 7β-hydroxylation of 5-ene and 5α-dihydro C19-steroids?
  作者：Natalia Milecka-Tronina、Teresa Kołek、Alina Świzdor、Anna Panek

  DOI：10.1016/j.bmc.2013.11.050

  日期：2014.1

  coerulea AM93. DHEA and androstenediol were transformed to the mixture of allyl 7-hydroxy derivatives, while EpiA and 5α-androstan-3,17-dione were converted mainly to 7α- and 7β-alcohols accompanied by 9α- and 11α-hydroxy derivatives. On the basis of (i) time course analysis of hydroxylation of the abovementioned substrates, (ii) biotransformation with resting cells at different pH, (iii) enzyme inhibition

  在本文中，我们着重研究了Absidia coerulea AM93对DHEA，雄烯二醇，表雄甾酮和5α-雄烷-3,17-二酮进行7-羟基化的过程。除此之外，我们提出了对蓝藻中类固醇的羟基化的初步分析。AM93。DHEA和雄烯二醇被转化为烯丙基7-羟基衍生物的混合物，而EpiA和5α-雄烷-3,17-二酮主要转化为7α-和7β-醇，并伴有9α-和11α-羟基衍生物。基于（i）上述底物羟基化的时程分析，（ii）在不同pH下静息细胞的生物转化，（iii）酶抑制分析以及（iv）底物C–H键之间的几何关系经历羟基化和辅因子结合的活性氧原子，但假定相同的酶可催化氧化ç 7 -H α以及为C 7 -H β在-5-烯和5α二氢C键19-类固醇。在底物的结构和羟基化的区域选择性之间观察到的相关性表明，正常的结合酶-底物复合物中可能发生7β-羟基化，而在反向反向结合复合物中则发生7α-羟基化。
• Microbial hydroxylation of some steroids by Aspergillus wentii MRC 200316
  作者：Kudret Yildirim

  DOI：10.1135/cccc2010112

  日期：——

  Biotransformations of epiandrosterone (1), dehydroepiandrosterone (2) and pregnenolone (3) byAspergillus wentiiMRC 200316 for 5 days have been reported. Incubation of epiandrosterone (1) afforded 11α-hydroxy-5α-androstane-3,17-dione (4) and 3β,11α-dihydroxy-5α-androstan-17-one (5). Incubation of dehydroepiandrosterone (2) afforded 3β,7β-di-hydroxyandrost-5-en-17-one (6) and 3β,7α-dihydroxyandrost-5-en-17-one (7). Incubation of pregnenolone (3) afforded only 11α-hydroxypregn-4-ene-3,20-dione (8).

  对雄烯二酮（1）、去氢表雄酮（2）和孕酮（3）的生物转化已经报道，由Aspergillus wentiiMRC 200316在5天内进行。雄烯二酮（1）的培养产生11α-羟基-5α-雄烷-3,17-二酮（4）和3β,11α-二羟基-5α-雄烷-17-酮（5）。去氢表雄酮（2）的培养产生3β,7β-二羟基雄-5-烯-17-酮（6）和3β,7α-二羟基雄-5-烯-17-酮（7）。孕酮（3）的培养只产生11α-羟基孕-4-烯-3,20-二酮（8）。