(+/-)-(1α,4aβ,8aβ,10aα)-3,4,4a,6,7,8,8a,9,10,10a-decahydro-1,4a,8a-trimethylphenanthren-2(3H)-one | 141396-82-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (+/-)-(1α,4aβ,8aβ,10aα)-3,4,4a,6,7,8,8a,9,10,10a-decahydro-1,4a,8a-trimethylphenanthren-2(3H)-one
• 英文别名: (+/-)-(1S,4aS,8aR,10aS)-1,4a,8a-trimethyl-3,4,4a,6,7,8,8a,9,10,10a-decahydrophenanthren-2(1H)-one
• CAS: 141396-82-9
• 化学式: C₁₇H₂₆O
• 分子量: 246.393
• InChiKey: AUZCCHGAERUHLH-UTJXIGIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.52
• 重原子数：
  18.0
• 可旋转键数：
  0.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  (+/-)-(1α,4aβ,8aβ,10aα)-3,4,4a,6,7,8,8a,9,10,10a-decahydro-1,4a,8a-trimethylphenanthren-2(3H)-one 在 lithium tri-sec-butylaluminum hydride 作用下， 以 四氢呋喃 为溶剂， 以75%的产率得到(1R,2S,4aR,8aS,10aR)-1,4a,8a-Trimethyl-1,2,3,4,4a,6,7,8,8a,9,10,10a-dodecahydro-phenanthren-2-ol
  参考文献：
  名称：

  Remote oxidation of perhydrophenanthrenes by template-directed hydrogen atom abstraction.

  摘要：

  The use of Breslow's remote functionalization paradigm for installation of an axial C-7 hydroxy group into a perhydrophenanthrene nucleus, with a view toward synthesis of bruceantin (1), has been investigated. The substrates that were evaluated were 9a-c, 11, 17, 18, and 20. Substrates 9a-c all undergo preferential functionalization at C-12. After oxidative cleavage of the initial photoproduct, ketones 18a-c were obtained in yields of 18-26% (36-41%, based on unrecovered starting material). Unsaturated substrate 11 undergoes remote functionalization exclusively at the secondary allylic position (C-12); enone 20 is obtained in 83% overall yield after oxidative cleavage of the initial photoadduct, 19a,b. Thus, in this system, C-12 appears to be the preferred site of intramolecular functionalization. Attempts to block reaction at this position by the use of saturated ketone 18, the derived ketal 17, or enone 20, were all unsuccessful. In the case of 18 the only photoproduct was the intramolecular pinacol. Enone 20 gave an exceedingly complex mixture, consisting of many products. Ketal 17 afforded the unusual macrocyclic lactone 21 in 33% yield. The main conclusion of this study is that it is difficult to extrapolate from the excellent regioselectivity observed by Breslow in the steroid system to the trans-anti-trans perhydrophenanthrene system, which is only slightly less rigid. A second factor which we believe is important in the system we have studied is the apparently minor perturbation of having an equatorial substituent at C-4. We postulate that this substituent, which was not present in the model steroidal systems investigated previously by Breslow, disfavors functionalization at C-7.

  DOI：

  10.1021/jo00040a050
• 作为产物：
  描述：

  (+/-)-(4aR,8aS)-(4aα,8aα)-4,4a,6,7,8,8a,9,10-octahydro-1,4a,8a-trimethylphenanthren-2(3H)-one 在 氨 、 lithium 、 碘甲烷 作用下， 以 四氢呋喃 为溶剂， 以44%的产率得到(+/-)-(1α,4aβ,8aβ,10aα)-3,4,4a,6,7,8,8a,9,10,10a-decahydro-1,4a,8a-trimethylphenanthren-2(3H)-one
  参考文献：
  名称：

  Tricyclic-bis-enone derivatives and methods of use thereof

  摘要：

  提供了新型三环双烯酮衍生物（TBEs）以及制备此类TBEs的方法。还提供了用于预防和/或治疗癌症、阿尔茨海默病、帕金森病、多发性硬化症、肌萎缩侧索硬化、类风湿性关节炎、炎症性肠病以及所有其他疾病的方法，这些疾病的发病机制被认为涉及过量产生一氧化氮（NO）或前列腺素或iNOS或COX-2基因或基因产物的过度表达。此外，本发明的TBE化合物的合成方法利用廉价的商业可获得试剂，具有高成本效益且易于扩展。还提供了利用新型中间体的高效合成方法以及这些中间体的合成。此外，本发明还提供了设计新型水溶性TBEs的方法。

  公开号：

  US20030232786A1

文献信息

• Efficient synthesis of (−)- and (+)-tricyclic compounds with enone functionalities in rings A and C. A novel class of orally active anti-inflammatory and cancer chemopreventive agents
  作者：Tadashi Honda、Frank G. Favaloro, Jr.、Tomasz Janosik、Yukiko Honda、Nanjoo Suh、Michael B. Sporn、Gordon W. Gribble

  DOI：10.1039/b307491a

  日期：——

  desired to synthesize optically active TBE compounds for a comparison of the biological potency of both enantiomers. We now describe the synthesis of both enantiomers of (4a[small beta],8a[small beta],10a[small alpha])-1,2,4a,6,8a,9,10,10a-octahydro-1,1,4a,8a-tetramethyl-2,6-dioxophenanthren e-3-carbonitrile (2) and 3 from commercially available simple compounds. Interestingly, (+)-3 having the same

  根据合成的三萜类化合物2-氰基-3,12-二氧代油酸酯-1,9（11）的结构设计了在环A和环C具有烯酮官能团的新型三环化合物[三环-双-烯酮（TBE）化合物]。 ）-二烯-28-油酸（CDDO）（1），它是预防和/或治疗癌症和炎症性疾病的有前途的候选药物，其发病机理可能涉及一氧化氮（NO）和/或前列腺素的过量生产。一系列外消旋形式的TBE化合物显示出对小鼠巨噬细胞中干扰素-γ（IFN-γ）诱导的NO产生的高抑制活性。这些化合物之一，（+/-）-（4a [小β，8a [小β，10a [小α]）-1,2,4a，6,8a，9,10,10a-八氢-1 ，1,4a，8a-tetramethyl-2,6-dioxophenanthren e-3,7-dicarbonitrile（（+/-）-3），在一项初步研究中，使用硫代乙醇酸酯和IFN-γ诱导的小鼠腹膜炎症，口服活性为15 mg kg（-1）（单次