3-methoxy-D-homoestra-1,3,5(10),17-tetraene | 123827-06-5

• 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: 3-methoxy-D-homoestra-1,3,5(10),17-tetraene
• 英文别名: (4aS,4bS,10bS,12aR)-8-methoxy-12a-methyl-4,4a,4b,5,6,10b,11,12-octahydro-3H-chrysene
• CAS: 123827-06-5
• 化学式: C₂₀H₂₆O
• 分子量: 282.426
• InChiKey: WYFGEVONCXXPNO-ZRNYENFQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.9
• 重原子数：
  21
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  3-methoxy-D-homoestra-1,3,5(10)-triene-17β,17αβ-diol 在 titanium(III) chloride 作用下， 以 二乙二醇二甲醚 为溶剂， 反应 36.0h， 以92%的产率得到3-methoxy-D-homoestra-1,3,5(10),17-tetraene
  参考文献：
  名称：

  New low-valent titanium reagents for dicarbonyl coupling and their use in a general method of annulation

  摘要：

  New low-valent titanium reagents have been prepared by reducing TiCl3 (1 mol) with C8K (2 mol) or by reducing TiCl4 (1 mol) with Na-naphthalene (2.75 mol). Ketones carrying a chain that incorporates a suitably placed oxo function (aldehyde or ketone) undergo intramolecular dicarbonyl coupling to produce a bicyclic compound when treated with an excess (16-17 mol of titanium halide per mol of dicarbonyl compound) of one of these reagents. The procedure works well even for highly oxygenated substrates and constitutes a general method of annulation. Other reducing agents besides C8K or Na-naphthalene are suitable, and a brief examination of Na(Hg) and Na-K alloy was made. The C8K/TiCl3 system was also used to convert a cis-1,2-diol into the corresponding olefin.

  DOI：

  10.1021/jo00022a042

文献信息

• Use of radical ring opening for introduction of alkyl and substituted alkyl groups with stereochemical control: a synthetic application of cyclopropylcarbinyl radicals
  作者：Derrick L. J. Clive、Sylvain Daigneault

  DOI：10.1021/jo00012a009

  日期：1991.6

  Cyclopropylcarbinols 2a and 2b (see Scheme I), which are accessible by a number of routes, can be converted into the corresponding radicals 3a and 3b, respectively. These radicals undergo peripheral ring-opening of the cyclopropyl substructure to afford substituted cycloalkenes 4a and 4b. The whole sequence represents a general method for attaching alkyl, and substituted alkyl, groups to an existing cyclic structure, and it can often be carried out with predictable stereo- and regiochemical control. Reaction conditions for the ring-opening depend on the substitution pattern of the cyclopropane: where the non-bridgehead carbon of the cyclopropane carries a strongly electron-withdrawing group, the ring-opening can be done at the reflux temperature of benzene. However, in the absence of such electron-withdrawing groups, a low temperature is best used in order to suppress ring expansion. Various methods that accommodate these requirements are available for generating the radicals.
• New low-valent titanium reagents for dicarbonyl coupling and their use in a general method of annulation
  作者：Derrick L. J. Clive、Chengzhi Zhang、K. S. Keshava Murthy、William D. Hayward、Sylvain Daigneault

  DOI：10.1021/jo00022a042

  日期：1991.10

  New low-valent titanium reagents have been prepared by reducing TiCl3 (1 mol) with C8K (2 mol) or by reducing TiCl4 (1 mol) with Na-naphthalene (2.75 mol). Ketones carrying a chain that incorporates a suitably placed oxo function (aldehyde or ketone) undergo intramolecular dicarbonyl coupling to produce a bicyclic compound when treated with an excess (16-17 mol of titanium halide per mol of dicarbonyl compound) of one of these reagents. The procedure works well even for highly oxygenated substrates and constitutes a general method of annulation. Other reducing agents besides C8K or Na-naphthalene are suitable, and a brief examination of Na(Hg) and Na-K alloy was made. The C8K/TiCl3 system was also used to convert a cis-1,2-diol into the corresponding olefin.