17α-trimethylsilylacetylenyl-3-methoxy-1,3,5(10)-estratrien-17β-ol | 50866-94-9

• 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: 17α-trimethylsilylacetylenyl-3-methoxy-1,3,5(10)-estratrien-17β-ol
• 英文别名: (8R,9S,13S,14S,17S)-3-methoxy-13-methyl-17-(2-trimethylsilylethynyl)-7,8,9,11,12,14,15,16-octahydro-6H-cyclopenta[a]phenanthren-17-ol
• CAS: 50866-94-9
• 化学式: C₂₄H₃₄O₂Si
• 分子量: 382.618
• InChiKey: APJYMVYLSFKLTB-URYYLNOGSA-N

物化性质

• 沸点：
  474.8±45.0 °C(Predicted)
• 密度：
  1.08±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.16
• 重原子数：
  27
• 可旋转键数：
  3
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  17α-trimethylsilylacetylenyl-3-methoxy-1,3,5(10)-estratrien-17β-ol 在 carbon monoxide,cobalt,cyclopenta-1,3-diene 作用下， 以 xylene 为溶剂， 反应 12.0h， 以48%的产率得到3-甲氧基雌酮
  参考文献：
  名称：

  Synthesis of Terpene and Steroid Dimers and Trimers Having Cyclobutadienyl−Co and Aromatic Tethers

  摘要：

  The reaction of natural product derived propargylic alcohols with CpCo(CO)(2) produces three new types of natural product hybrids having two or three terpene or steroid fragments. The tether joining the natural product subunits is built during the reaction. Type 1 hybrids have two terpene or steroid moieties joined by a CpCo-cyclobutadiene tether, with the two units disposed in a 1,2-arrangement (9, 14, 22). Type 2 hybrids have a Co-cyclopentadienone tether (10). Type 3 has three units of terpene or steroid joined to a benzene ring (11, 12, 15). An unusual Co-mediated beta-carbon elimination pathway of propargylic alcohols leading to ketones (an unknown process in this chemistry) has been observed.

  DOI：

  10.1021/jo0703698
• 作为产物：
  描述：

  美雌醇 在 盐酸 、 正丁基锂 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 反应 77.0h， 生成 17α-trimethylsilylacetylenyl-3-methoxy-1,3,5(10)-estratrien-17β-ol
  参考文献：
  名称：

  Synthesis of Terpene and Steroid Dimers and Trimers Having Cyclobutadienyl−Co and Aromatic Tethers

  摘要：

  The reaction of natural product derived propargylic alcohols with CpCo(CO)(2) produces three new types of natural product hybrids having two or three terpene or steroid fragments. The tether joining the natural product subunits is built during the reaction. Type 1 hybrids have two terpene or steroid moieties joined by a CpCo-cyclobutadiene tether, with the two units disposed in a 1,2-arrangement (9, 14, 22). Type 2 hybrids have a Co-cyclopentadienone tether (10). Type 3 has three units of terpene or steroid joined to a benzene ring (11, 12, 15). An unusual Co-mediated beta-carbon elimination pathway of propargylic alcohols leading to ketones (an unknown process in this chemistry) has been observed.

  DOI：

  10.1021/jo0703698

文献信息

• One-pot ethynylation and catalytic desilylation in synthesis of mestranol and levonorgestrel
  作者：Fung Fuh Wong、Shih Hsien Chuang、Sheng-chuan Yang、Yu-Hsiang Lin、Wen-Che Tseng、Shao-Kai Lin、Jiann-Jyh Huang

  DOI：10.1016/j.tet.2010.04.008

  日期：2010.6

  both in 90% yields. A plausible mechanism was proposed for the catalytic desilylation through the regeneration of the fluoride ion from the reaction of alkoxide on the steroid with Me3SiF. The one-pot ethynylation and catalytic desilylation methodology provided an alternative route and avoided the traditional use of flammable and explosive acetylene gas toward the synthesis of mestranol and levonorgestrel

  开发了一锅法乙炔基化和催化脱甲硅基反应来合成甲雌醇和左炔诺孕酮。在甾族化合物的C-17处的羰基上加三甲基甲硅烷基乙炔化物可制得C-17α-三甲基甲硅烷基乙炔基加合物，在一个锅中用催化量的TBAF（0.050当量）将其甲硅烷基化，从而得到90％的相应的雌三醇和左炔诺孕酮产量。有人提出了一种合理的机理，可以通过甾族化合物上的醇盐与Me 3 SiF的反应中的氟离子的再生来催化甲硅烷基化。单锅乙炔化和催化去甲硅烷基化方法提供了另一种途径，避免了传统的使用易燃易爆乙炔气来合成雌二醇和左炔诺孕酮。
• Steroidal silicon side-chain analogs as potential antifertility agents
  作者：Richard H. Peters、David F. Crowe、Masato Tanabe、Mitchell A. Avery、Wesley K. M. Chong

  DOI：10.1021/jm00387a011

  日期：1987.4

  A number of silicon-substituted analogues of ethynylestradiol that exhibit modified and enhanced biological activities have been synthesized. Particularly noteworthy are a group of [(trialkylsilyl)ethynyl]estradiol analogues that exhibit high antifertility potency and markedly reduced estrogenic activity. The best compounds synthesized are 17 alpha-[(triethylsilyl)ethynyl]estradiol (5) and 17 alpha-[(tert-butyldimethylsilyl)ethynyl]estradiol (33), which show a separation of antifertility from estrogenic activity in the rat. The results of structure-activity studies indicate a good correlation between the observed biological activities and the calculated van der Waals volumes of the three variable silicon substituents.