19-(tert-butyldimethylsiloxy)androst-5-en-17-one | 157022-94-1

• 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: 19-(tert-butyldimethylsiloxy)androst-5-en-17-one
• 英文别名: (8R,9S,10S,13S,14S)-10-[[tert-butyl(dimethyl)silyl]oxymethyl]-13-methyl-1,2,3,4,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-17-one
• CAS: 157022-94-1
• 化学式: C₂₅H₄₂O₂Si
• 分子量: 402.693
• InChiKey: WFTCMHSFBSXITC-MNUZBTPPSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.91
• 重原子数：
  28
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  19-(tert-butyldimethylsiloxy)androst-5-en-17-one 在 高氯酸 、 jones reagent 、 乙醇 、 溴 、 对甲苯磺酸 、 溶剂黄146 、 calcium carbonate 、 锌 、 N-溴代乙酰胺 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 丙酮 为溶剂， 反应 23.4h， 生成 19-acetoxyandrost-5-ene-4,17-dione
  参考文献：
  名称：

  芳香酶竞争性抑制剂5-雄烯-4,17-二酮的19-氧化衍生物的合成。

  摘要：

  由19-（叔丁基二甲基甲硅烷氧基）androst-5合成了19-羟基-甾醇13和19-oxo-甾族化合物13和15，它们是芳香酶抑制剂5-雄甾烯-4,17-二酮（3）的潜在代谢物。 -en-17-one（5）或4beta-acetoxyandrost-5-en-17-one（16），分别通过5alpha-bromo-4beta-hydroxy-6beta，19-epoxyandrostan + ++-17-one（10）作为每个序列中的关键中间体。19-甲硅烷氧基化合物5与Br2的反应生成5α-溴-6β，19-环氧化合物8，将其用N，N'-二甲基乙酰胺处理，然后与N-溴乙酰胺和0.28 M HCIO4反应，得到化合物10。另一方面，用N-溴乙酰胺-HClO 4处理4β-乙酰氧基甾族化合物16，然后在辐射下用Pb（IV）乙酸和I 2氧化，再用K 2 CO 3水解，也制得化合物10，产率比上述合成更好。琼斯氧化4beta-ol

  DOI：

  10.1016/s0039-128x(98)00113-5
• 作为产物：
  描述：

  3β-<(p-tolylsulfonyl)oxy>-19-(tert-butyldimethylsiloxy)androst-5-en-17-one 在 水 、 sodium iodide 、 锌 作用下， 以 乙二醇二甲醚 为溶剂， 反应 3.5h， 以86%的产率得到19-(tert-butyldimethylsiloxy)androst-5-en-17-one
  参考文献：
  名称：

  Synthesis of Androst-5-en-7-ones and Androsta-3,5-dien-7-ones and Their Related 7-Deoxy Analogs as Conformational and Catalytic Probes for the Active Site of Aromatase

  摘要：

  A series of androst-5-en-7-ones and androsta-3,5-dien-7-ones and their 7-deoxy derivatives, respectively, were synthesized and tested for their abilities to inhibit aromatase in human placental microsomes. All the steroids inhibited the enzyme in a competitive manner with K-i's ranging from 0.058 to 45 mu M. The inhibitory activities of 17-oxo compounds were much more potent than those of the corresponding 17 beta-alcohols in each series. Steroids having an oxygen function (hydroxy or carbonyl) at C-19 were less potent inhibitors than the corresponding parent compounds having a 19-methyl group. 3,5-Dien-7-one 24 and its 19-hydroxy and 19-oxo derivatives (12 and 13) as well as 19-oxo-5-en-7-one 3 caused a time-dependent inactivation of aromatase only in the presence of NADPH in which the k(inact) values of 19-als 3 and 13 (0.143 and 0.189 min(-1), respectively) were larger than those of the corresponding 19-methyl (23 and 24) and 19-hydroxy (1 and 12) steroids, respectively. 19-Nor-5-en-7-one 4 but not its 3,5-diene derivative 14 also inactivated the enzyme in a time-dependent manner. In contrast, 7-deoxy steroids 21 and 27, having a 19-methyl group, did not cause it. The inactivations were prevented by the substrate androstenedione, and no significant effects of L-cysteine on the inactivations were observed in each case. The results suggest that oxygenation at C-19 would be at least in part involved in the inactivations caused by the inhibitors 23 and 24. The conjugated enone structures should play a critical role in the inactivation sequences.

  DOI：

  10.1021/jm00040a012