(1R,4aR,8aR,10aR)-1,4a-Dimethyl-2-oxo-1,3,4,4a,6,7,8,9,10,10a-decahydro-2H-phenanthrene-8a-carboxylic acid methyl ester | 141396-80-7

• 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: (1R,4aR,8aR,10aR)-1,4a-Dimethyl-2-oxo-1,3,4,4a,6,7,8,9,10,10a-decahydro-2H-phenanthrene-8a-carboxylic acid methyl ester
• CAS: 141396-80-7
• 化学式: C₁₈H₂₆O₃
• 分子量: 290.403
• InChiKey: KBSWNXDDIVFJSR-XHSVMWQWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.67
• 重原子数：
  21.0
• 可旋转键数：
  1.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  43.37
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  (1R,4aR,8aR,10aR)-1,4a-Dimethyl-2-oxo-1,3,4,4a,6,7,8,9,10,10a-decahydro-2H-phenanthrene-8a-carboxylic acid methyl ester 在 4-二甲氨基吡啶 、 lithium tri-sec-butylaluminum hydride 、 N,N'-二环己基碳二亚胺 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 9.17h， 生成 (1R,2S,4aR,8aR,10aR)-2-[3-(4-Benzoyl-phenyl)-propionyloxy]-1,4a-dimethyl-1,3,4,4a,6,7,8,9,10,10a-decahydro-2H-phenanthrene-8a-carboxylic acid methyl ester
  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,8aR)-1,4a-Dimethyl-2-oxo-3,4,4a,6,7,8,9,10-octahydro-2H-phenanthrene-8a-carboxylic acid methyl ester 在 LiSnCu 、 叔丁醇 作用下， 以 四氢呋喃 、 氨 为溶剂， 反应 1.5h， 以84%的产率得到(1R,4aR,8aR,10aR)-1,4a-Dimethyl-2-oxo-1,3,4,4a,6,7,8,9,10,10a-decahydro-2H-phenanthrene-8a-carboxylic acid methyl ester
  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

文献信息

• Synthetic Studies on Quassinoids:  Total Synthesis and Biological Evaluation of (+)-Des-<scp>d</scp>-chaparrinone
  作者：Paul A. Grieco、Jason D. Speake

  DOI：10.1021/jo980571y

  日期：1998.8.1

  A total synthesis of des-D-chaparrinone (2), which lacks the ring D delta-lactone of (-)-chaparrinone (1) has been developed. The synthesis commences with the known, readily available tricyclic ketone 3 (R = Me). Elaboration of the configuration at C(5) followed by resolution of 6 employing 2(R),3(R)-2,3-butanediol gave rise to 9. Installation of the ring C functionality provided 15 which was transformed

  已经开发了缺少（-）-查帕瑞酮（1）的D环δ-内酯的des-D-查帕瑞酮（2）的全合成。合成从已知的，容易获得的三环酮3（R = Me）开始。阐述在C（5）处的构型，然后使用2（R），3（R）-2,3-丁二醇拆分为6，得到9。环C官能度的安装提供了15，其转化为三环二酮25引入环A官能团得到29，其在暴露于三氯化铝和碘化钠时直接产生（+）-des-D-查帕瑞酮（2）。生物学研究表明（+）-2没有任何实体瘤活性。