(+/-)-2,3,3a,4,5,7,8,9,9aβ,9bα-Decahydro-3aβ,6-dimethyl-3β-hydroxy-7-oxo-1H-benzinden | 13652-05-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-2,3,3a,4,5,7,8,9,9aβ,9bα-Decahydro-3aβ,6-dimethyl-3β-hydroxy-7-oxo-1H-benzinden
• 英文别名: (+/-)-3β-Hydroxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-3aβ,6-dimethyl-1H-benzinden-7-on；(+/-)-17β-Hydroxy-des-A-androst-9-en-5-on；rac-17β-Hydroxy-des-A-9-androsten-5-on；(+/-)-3β-Hydroxy-2,3,3a,4,5,7,8,9,9aβ,9bα-decahydro-3aβ,6-dimethyl-1H-benz[e]inden-7-on；(3S,3aS,9aS,9bS)-3-hydroxy-3a,6-dimethyl-2,3,4,5,8,9,9a,9b-octahydro-1H-cyclopenta[a]naphthalen-7-one
• CAS: 13652-05-6；14030-26-3；40762-81-0；57884-53-4；83646-91-7
• 化学式: C₁₅H₂₂O₂
• 分子量: 234.338
• InChiKey: DCEFUYKVMXITER-DHMWGJHJSA-N

物化性质

• 沸点：
  377.2±42.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.85
• 重原子数：
  17.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  37.3
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (+/-)-2,3,3a,4,5,7,8,9,9aβ,9bα-Decahydro-3aβ,6-dimethyl-3β-hydroxy-7-oxo-1H-benzinden 在 甲醇 、 sodium hydroxide 、 sodium tetrahydroborate 、 potassium tert-butylate 、 乙酸酐 、 间氯过氧苯甲酸 、 pyridinium chlorochromate 作用下， 生成 (3S,3aS,9aS,9bS)-3-(tert-butoxy)-3a,6-dimethyl-2,3,3a,4,8,9,9a,9b-octahydro-1H-cyclopenta[a]naphthalene-5,7-dione
  参考文献：
  名称：

  Reductive alkylation of enediones. 2. Synthesis of corticosteroids

  摘要：

  DOI：

  10.1021/ja00523a079
• 作为产物：
  描述：

  <3aS-(3aα,9aα,9bβ)>-3a,4,5,9,9a,9b-hexahydro-3a,6-dimethyl-1H-benzindene-3,7(2H,8H)-dione 在 lithium tri-t-butoxyaluminum hydride 作用下， 生成 (+/-)-2,3,3a,4,5,7,8,9,9aβ,9bα-Decahydro-3aβ,6-dimethyl-3β-hydroxy-7-oxo-1H-benzinden
  参考文献：
  名称：

  类固醇全合成。二。（-）-17-羟基-des-A-androst-9-en-5-one。

  摘要：

  AbstractBased on the results obtained in the racemic series (part I), (—)‐17β‐hydroxy‐des‐A‐androst‐9‐en‐5‐one has been synthesized, starting with (S)‐(—)‐5‐heptanolide. The key step, viz. the condensation of (S)‐(—)‐7‐hydroxy‐1‐nonen‐3‐one (or its amine adduct) with 2‐methyl‐cyclopentane‐1, 3‐dione involves an asymmetric induction. Model experiments with (R)‐(+)‐5‐decanolide leading to the enantiomeric homolog of the BCD‐tricyclic compound are also described.

  DOI：

  10.1002/hlca.19710540746

文献信息

• Total synthesis of optically active (−)17β-hydroxy-Δ9(10)-desA-androsten-5-one
  作者：Z.G. Hajos、D.R. Parrish、E.P. Oliveto

  DOI：10.1016/s0040-4020(01)82508-4

  日期：1968.1

  aβ-methyl-5(6H)-indanone was resolved via the hydrogen phthalate-brucine salt. The dextrorotatory enantiomer (+)4 was then converted in a 5-step stereospecific total synthesis to the important BCD tricyclic intermediate (−)13. The synthesis also adds additional proof for the absolute configuration of the bicyclic keto alcohol (+)4 by correlation with (±_13, a known degradation product of natural steroids

  通过邻苯二甲酸氢溴酸氢溴酸盐拆分（±）7,7a-二氢-1β-羟基-7aβ-甲基-5（6H）-茚满酮。然后将右旋对映异构体（+）4在5步立体定向总合成中转化为重要的BCD三环中间体（-）13。该合成还通过与（±_ 13）已知的天然类固醇降解产物的相关性，为双环酮醇（+）4的绝对构型提供了额外的证据。
• Versuche zur Synthese von 9β, 10α-Steroiden; B,C,D-tricyclische Verbindungen
  作者：G. Saucy、W. Koch、M. Müller、A. Fürst

  DOI：10.1002/hlca.19700530512

  日期：——

  In a search for a new and efficient synthesis of the compound 7, the cyclization of 5 (obtained by a Michael-reaction from 3 and 4) was studied. Treatment of 5 with strong acid furnished the known dienedione 8. Mild acidic conditions gave the bridged alcohol 9 and other, unidentified products, rather than the desired enone 6. Under basic conditions, 5 did not cyclize to 6, but underwent retro-Michael

  在该化合物的一种新的和有效的合成的搜索7，的环化5（由获得的迈克尔从-反应3和4）进行了研究。用强酸处理5可得到已知的二烯二酮8。温和的酸性条件使桥连的醇9和其他身份不明的产品，而不是所需的烯酮6。在基本条件下，5并没有环化为6，而是经历了Michael逆反应。然后尝试将二烯二酮8转化为14α-烯酮19。但是，催化加氢和锂氨还原反应均为8，主要产生14β产物。在一些氢化实验中，二烯二酮8异构化成苯酚13（主要）和14（次要）。通过化学和光谱法确定了新的异构体des-A-androst-9-en-5，17-二酮（16、17和20）的立体化学。
• Antiandrogenic activity of a series of des-A-steroid derivatives
  作者：Hilda Morales-Alanis、Marie Josephe Brienne、Jean Jacques、Marie M. Bouton、Lucien Nedelec、Vesperto Torelli、Colette Tournemine

  DOI：10.1021/jm00150a009

  日期：1985.12

  In the search for new antiandrogens, a number of des-A-steroids were prepared by condensation of Grignard reagents with lactone 3. From the resulting key intermediates 5, various structural modifications were performed such as the introduction of an additional unsaturation to afford dienones 8 and aromatic derivatives 10 or the introduction of an alkyl substituent mostly in position 10 (11-13) but also in some cases in position 16 (22). In addition, 13-ethyl analogues were also prepared from lactone 4. The relative binding affinities (RBAs) for the androgen receptor of these compounds were determined under various conditions. Some compounds exhibit a capacity to interact with the receptor comparable to that of testosterone. One of the most potent compounds is 17beta-hydroxy-des-A-androsta-9,11-dien-5-one (8b), RBA value 73% of that of testosterone. More interestingly, several compounds were found to have an antiandrogenic profile in vitro and in vivo. One of the most effective compounds is 10-ethyl-17beta-hydroxy-des-A-estra-9-en-5-one (5c), which exhibits a strong local antiandrogenic activity in hamsters, without any significant systemic antiandrogenic effects. The corresponding 17beta-acetyl derivative (RU 38882) has been selected for extended pharmacological studies.
• Steroid Total Synthesis, Part III. 9?, 10?-Testosterone
  作者：G. Saucy、R. Borer

  DOI：10.1002/hlca.19710540815

  日期：1971.12.10

  AbstractThe total synthesis of 9β, 10α‐testosterone via a BCD‐tricyclic intermediate is described. The latter compound – 17β‐hydroxy‐des‐A‐androst‐9‐en‐5‐one – was obtained in optically active form by our previously reported scheme, using an efficient resolution step early in the synthesis. New results regarding the asymmetric induction step are also discussed.
• Totalsynthese von Steroiden. 1. Mitteilung.<i>rac</i>-17β-Hydroxydes-A-androst-9-en-5-on
  作者：G. Saucy、R. Borer、A. Fürst

  DOI：10.1002/hlca.19710540734

  日期：1971.11.1

  AbstractIn connection with earlier work on the synthesis of 9β, 10α‐steroids, a new and practical synthesis of rac‐17α‐hydroxy‐des‐A‐androst‐9‐en‐5‐one (19) has been developed, based on a novel stereoselective condensation of 7‐hydroxy‐1‐nonen‐3‐one (3) with 2‐methyl‐cyclopentane‐1, 3‐dione (9) and subsequent transformations of the resulting tricyclic diene ether 12.