3α,5-cycloandrost-6-en-17-one | 1224-07-3

• 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: 3α,5-cycloandrost-6-en-17-one
• 英文别名: (1S,2R,5R,7S,10R,11S,15S)-2,15-dimethylpentacyclo[8.7.0.02,7.05,7.011,15]heptadec-8-en-14-one
• CAS: 1224-07-3
• 化学式: C₁₉H₂₆O
• 分子量: 270.415
• InChiKey: CXSUFSNPGRCCLJ-OYGYLSKNSA-N

物化性质

• 熔点：
  139 °C
• 沸点：
  375.4±21.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  20
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.84
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3α,5-cycloandrost-6-en-17-one 在 四氧化锇 作用下， 生成 6β,7β-dihydroxy-3α,5α-cycloandrostan-17-one
  参考文献：
  名称：

  Hanson, James R.; Knights, Steve G., Journal of the Chemical Society. Perkin transactions I, 1980, p. 1306 - 1310

  摘要：

  DOI：
• 作为产物：
  描述：

  3β-tosyloxyandrost-5-ene-17-one 生成 3α,5-cycloandrost-6-en-17-one
  参考文献：
  名称：

  Analytical Chemical Studies on Steroids. VII. The Zimmermann Complexes Derived from i-Androstanolone and Its Related 17-Oxosteroids

  摘要：

  研究了由i-雄甾烷酮（6β-羟基-3α，5α-环雄甾-17-酮）生成的齐默尔曼复合物的结构。通过制备薄层色谱法，成功分离出两种复合物，并分别阐明其为 6β-hydroxy-16ξ-(2, 4-dinitrophenyl)-3α, 5α-cycloandrostan-17-one, m.p. 113∼116° 和 3β-chloro-16ξ-(2, 4-dinitrophenyl)androst-5-en-17-one, m.p. 192∼194°。这些结果表明，前一种复合物与盐酸接触后会转化为后一种复合物。另一方面，脱氢异雄酮生成的齐默尔曼复合物为 3β-羟基-16ξ-（2，4-二硝基苯基）雄-5-烯-17-酮，熔点为 186∼188°。

  DOI：

  10.1248/cpb.13.1435

文献信息

• The microbiological hydroxylation of 3α,5-cycloandrostanes by Cephalosporium aphidicola
  作者：Caroline S. Bensasson、James R. Hanson、Yvan Le Huerou

  DOI：10.1016/s0031-9422(99)00415-x

  日期：1999.12

  The microbiological hydroxylation of some 3α,5-cycloandrostanes by the fungus, Cephalosporium aphidicola has been shown to take place at C-2α and C-14α and a 6β-alcohol was oxidized to the 6-ketone.

  真菌 Cephalosporium aphidicola 对某些 3α,5-环雄甾烷的微生物羟基化作用已显示在 C-2α 和 C-14α 处发生，并且 6β-醇被氧化为 6-酮。
• The scope and limitations of the reaction of δ5-steroids with mercury(II) trifluoroacetate
  作者：Peter L.D Ruddock、David J Williams、Paul B Reese

  DOI：10.1016/s0039-128x(98)00076-2

  日期：1998.12

  other mercury salts on the reaction were also studied. Treibs oxidation was successful in chloroform, carbon tetrachloride, and dibromomethane, but not in other solvents tested. 3β-Acetoxy-6-bromomercuriandrost-5-en-17-one was obtained in dibromomethane. Replacement of the reagent by mercury(II) trichloroacetate altered the intermediates formed but not the products. Mercury(II) tribromoacetate was unreactive

  摘要 研究了C-3 取代基对雄性5-烯与三氟乙酸汞(II) 在二氯甲烷中反应（改性Treibs 氧化）的影响。3β-Acyloxyandrost-5-en-17-ones 得到 3β-acyloxy-6β-hydroxyandrost-4-en-17-ones 伴随着 3β-acyloxy-6-chloromercuriandrost-5-en-17-ones。3β-Acetoxy-6β-trifluoroacetoxyandrost-4-en-17-one 和 3β-acetoxy-4β-trifluoroacetoxyandrost-5-en-17-one 是反应的中间体。氯汞类固醇的形成表明溶剂参与了反应。以 3α-acetoxyandrost-5-en-17-one 作为底物，观察到产物分布的完全逆转。3β-Haloandrost-5-en-17-ones 的主要产物反映了卤化物的
• Allyl‐Palladium‐Catalyzed Ketone Dehydrogenation Enables Telescoping with Enone α,β‐Vicinal Difunctionalization
  作者：Yifeng Chen、David Huang、Yizhou Zhao、Timothy R. Newhouse

  DOI：10.1002/anie.201704874

  日期：2017.7.3

  The telescoping of allyl‐palladium catalyzed ketone dehydrogenation with organocuprate conjugate addition chemistry allows for the introduction of aryl, heteroaryl, vinyl, acyl, methyl, and other functionalized alkyl groups chemoselectively to a wide variety of unactivated ketone compounds via their enone counterparts. The compatibility of the dehydrogenation conditions additionally allows for efficient

  烯丙基钯催化的酮脱氢与有机铜酸酯共轭加成化学的伸缩作用使芳基，杂芳基，乙烯基，酰基，甲基和其他官能化烷基可通过其对映异构体化学选择性地引入到各种未活化的酮化合物中。脱氢条件的相容性还允许中间烯醇与各种亲电试剂的有效捕集。通过与几个先前报告的多步骤序列进行比较，证明了该方法的实用性。
• Synthesis of Cyclic Enones by Allyl-Palladium-Catalyzed α,β-Dehydrogenation
  作者：David Huang、Yizhou Zhao、Timothy R. Newhouse

  DOI：10.1021/acs.orglett.7b03818

  日期：2018.2.2

  The use of allyl-palladium catalysis for the one-step α,β-dehydrogenation of ketones via their zinc enolates is reported. The optimized protocol utilizes commercially available Zn(TMP)2 as base and diethyl allyl phosphate as oxidant. Notably, this transformation operates under salt-free conditions and tolerates a diverse scope of cycloalkanones.

  报道了烯丙基钯催化通过酮的烯醇锌对酮进行α，β-脱氢的一步。优化后的协议利用市售的Zn（TMP）2作为碱，并使用磷酸二乙基烯丙酯作为氧化剂。值得注意的是，这种转化是在无盐条件下进行的，并能耐受各种环烷酮。
• Hydroxylation of steroids by Fusarium oxysporum, Exophiala jeanselmei and Ceratocystis paradoxa
  作者：Patrice C. Peart、Kayanne P. McCook、Floyd A. Russell、William F. Reynolds、Paul B. Reese

  DOI：10.1016/j.steroids.2011.06.010

  日期：2011.11

  The potential of Fusarium oxysporum var. cubense UAMH 9013 to perform steroid biotransformations was reinvestigated using single phase and pulse feed conditions. The following natural steroids served as substrates: dehydroepiandrosterone (1), pregnenolone (2), testosterone (3), progesterone (4), cortisone (5), prednisone (6), estrone (7) and sarsasapogenin (8). The results showed the possible presence of C-7 and C-15 hydroxylase enzymes. This hypothesis was explored using three synthetic androstanes: androstane-3,17-dione (9), androsta-4,6-diene-3,17-dione (10) and 3 alpha,5 alpha-cycloandrost-6-en-17-one (11). These fermentations of non-natural steroids showed that C-7 hydroxylation was as a result of that position being allylic. The evidence also pointed towards the presence of a C-15 hydroxylase enzyme.The eleven steroids were also fed to Exophiala jeanselmei var. lecanii-corni UAMH 8783. The results showed that the fungus appears to have very active 5 alpha and 14 alpha-hydroxylase enzymes, and is also capable of carrying out allylic oxidations.Ceratocystis paradoxa UAMH 8784 was grown in the presence of the above-mentioned steroids. The results showed that monooxygenases which effect allylic hydroxylation and Baeyer-Villiger rearrangement were active. However, redox reactions predominated. (C) 2011 Elsevier Inc. All rights reserved.