(6R,8R,9S,10R,13S,14S)-6-methoxy-10,13-dimethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[α]phenanthrene-3,17(2H,6H)-dione | 13163-89-8

• 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: (6R,8R,9S,10R,13S,14S)-6-methoxy-10,13-dimethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[α]phenanthrene-3,17(2H,6H)-dione
• 英文别名: 6β-methoxy-4-androstene-3,17-dione；6β-methoxyandrost-4-ene-3,17-dione；6β-methoxy-4-androsten-3,17-dione；6β-Methoxy-Δ⁴-androsten-3,17-dion；6β-Methoxy-3,17-dioxo-androsten-4；(6R,8R,9S,10R,13S,14S)-6-methoxy-10,13-dimethyl-2,6,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene-3,17-dione
• CAS: 13163-89-8；111266-35-4；13163-86-5
• 化学式: C₂₀H₂₈O₃
• 分子量: 316.441
• InChiKey: GXOLMLOJBNSABS-XOJMLDNQSA-N

物化性质

• 熔点：
  164-166 °C
• 沸点：
  458.5±45.0 °C(Predicted)
• 密度：
  1.13±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  23
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (6R,8R,9S,10R,13S,14S)-6-methoxy-10,13-dimethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[α]phenanthrene-3,17(2H,6H)-dione 在 碘硅烷 作用下， 以 氯仿 为溶剂， 反应 4.0h， 以88%的产率得到5α-androst-3,6,17-trione
  参考文献：
  名称：

  Numazawa, Mitsuteru; Mutsumi, Ayako; Ogata, Mieko, Chemical and pharmaceutical bulletin, 1988, vol. 36, # 9, p. 3381 - 3386

  摘要：

  DOI：
• 作为产物：
  描述：

  5α,6α-epoxy-17-oxoandrostan-3β-yl acetate 在 chromium(VI) oxide 、 氢氧化钾 、 硫酸 作用下， 以 甲醇 、 丙酮 为溶剂， 生成 (6R,8R,9S,10R,13S,14S)-6-methoxy-10,13-dimethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[α]phenanthrene-3,17(2H,6H)-dione
  参考文献：
  名称：

  Julia,S. et al., Bulletin de la Societe Chimique de France, 1966, p. 2277 - 2283

  摘要：

  DOI：

文献信息

• Convenient method for the functionalization of the 4- and 6-positions of the androgen skeleton
  作者：Daniel Morton、Allison R. Dick、Debashis Ghosh、Huw M. L. Davies

  DOI：10.1039/c2cc31973j

  日期：——

  The preparation and reactivity of steroidal vinyldiazo compounds is reported, providing a convenient, substituent tolerant, chemo- and stereoselective entry into 4- and 6-substituted androgen analogues from a common precursor. Under dirhodium catalysis, O–H insertion occurs at the carbenoid site, leading to 4-substituted steroids, but under silver catalysis, O–H insertion occurs at the vinylogous position, leading to 6-substituted steroids.

  本文报道了甾体乙烯基重氮化合物的制备和反应活性，提供了一种便捷、对取代基容忍、化学选择性和立体选择性的方法，从共同前体合成4-和6-取代的雄激素类似物。在双铑催化下，O–H插入发生在卡宾位点，生成4-取代的甾体，而在银催化下，O–H插入发生在乙烯位点，生成6-取代的甾体。
• Photochemical Reactions. 21. Sensitized Photooxygenation of<i>N</i>-Methylated 4-Aza-5-androsten-3-one and 4-Aza-5-androstene Steroidal Systems
  作者：Joan Francesc Piniella、Jordi Estapé、Pilar Lupón、Luis Merino、Mariano Puig、Juan-Julio Bonet、José Luis Briansó、Gabriel Germain

  DOI：10.1246/bcsj.60.3011

  日期：1987.8

  Two steroidal ene lactams, N-methyl-4-aza-5-androsten-3,17-dione and N-methyl-6-methoxy-4-aza-5-androsten-3,17-dione, and an enamine, N-methyl-4-aza-5-androsten-17β-ol, have been synthetized and their sensitized photooxygenations were investigated. The two ene lactams yield fragmentation compounds via the corresponding dioxetanes. Comparison with the previously reported behavior of an analogous N-unsubstituted ene lactam, seems to indicate that N-substitution is essential for the fragmentation to take place. On the other hand, the enamine yields a ketol. All results are briefly discussed from the mechanistic point of view.

  我们合成了两种甾体烯丙基内酰胺（N-甲基-4-氮杂-5-雄烯-3,17-二酮和 N-甲基-6-甲氧基-4-氮杂-5-雄烯-3,17-二酮）和一种烯胺（N-甲基-4-氮杂-5-雄烯-17β-醇），并研究了它们的敏化光氧化反应。这两种烯内酰胺通过相应的二氧杂环丁烷产生碎片化合物。与之前报道的一种类似的 N-未取代烯丙内酰胺的行为相比，似乎表明 N-取代是发生碎片化的必要条件。另一方面，烯胺产生了酮醇。本文从机理角度对所有结果进行了简要讨论。
• Methoxylation of enolizable steroidal 4-ene-3-ones using hypervalent iodine
  作者：Mitsuteru Numazawa、Mieko Ogata

  DOI：10.1039/c39860001092

  日期：——

  Reaction of androst-4-ene-3,17-dione (1) with o-iodosylbenzoic acid in methanolic potassium hydroxide gave the methoxylated products, the 4- and 6β-methoxides (2) and (3), along with the dehydrogenated compound, the 4,6-dienone (4).

  雄烷-4-烯-3,17-二酮（1）与邻碘烷基苯甲酸在甲醇氢氧化钾中反应制得甲氧基化产物，4-和6β-甲醇盐（2）和（3）以及脱氢化合物，4,6-二烯酮（4）。
• Probing the binding pocket of the active site of aromatase with 6-ether or 6-ester substituted androst-4-ene-3,17-diones and their diene and triene analogs
  作者：Mitsuteru Numazawa、Momoko Shelangouski、Mina Nagasaka

  DOI：10.1016/s0039-128x(00)00169-0

  日期：2000.12

  A series of 6-ester- (3 and 4) and 6-ether- (7 and 8) substituted androst-4-ene-3,17-diones (androstenediones) and their 1,4-diene analogs (5 and 6, and 9 and 10) as well as CB-substituted 4,6-diene and 1,4,6-triene steroids 11 and 12 were synthesized as aromatase inhibitors to gain insight into the structure-activity relationship between various substituents and inhibitory activity. All of the inhibitors synthesized blocked aromatase in a competitive manner. The inhibitory activities of all of the steroids, except for the 6 beta -benzoates 4g and 6h and the 6 beta -acetate 6a, were fairly effective to very powerful (K-i: 7.0 -320 nM). The 6 alpha -n-hexanoyloxy- and 6 alpha -benzyloxyandrostenediones (3e and 7e) were the most potent inhibitors (K-i: 7.0 nM each). In the series of 4-ene and 1,4-diene steroids, the 6 alpha -substituted steroids had higher affinity for the enzyme than the corresponding 6 beta -isomers. In the 1,4-diene steroid series, 6 beta -substituted steroids 6a, e, g, and 10a, b, e caused a time-dependent inactivation of aromatase, whereas their 6 alpha -isomers 5 and 9 essentially did not. The ether-substituted 1,4,6-trienes 12 inactivated the enzyme in a time-dependent manner; in contrast, their 4,6-diene analogs 11 did not. The substrate androstenedione blocked the inactivation, but no significant effect of L-cysteine was observed. Based on molecular modeling with the PM3 method, along with the present inhibition and inactivation results, it is thought that both the steric effects of the 6-substituents as well as the electronic effects of the C-6 oxygen functions play a critical role in the binding of inhibitors to the active site of aromatase. (C) 2000 Elsevier Science Inc. All rights reserved.
• Kocor,M.; Lenkowski,P., Bulletin de l'Academie Polonaise des Sciences, Serie des Sciences Chimiques, 1967, vol. 15, # 8, p. 329 - 333
  作者：Kocor,M.、Lenkowski,P.

  DOI：——

  日期：——