3β-hydroxy-18a,18b-dihomoandrost-5-en-17,18a-dione | 143882-51-3

• 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: 3β-hydroxy-18a,18b-dihomoandrost-5-en-17,18a-dione
• CAS: 143882-51-3
• 化学式: C₂₁H₃₀O₃
• 分子量: 330.467
• InChiKey: CHXKADCWAXHWFG-XRFJLBFOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.84
• 重原子数：
  24.0
• 可旋转键数：
  2.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  54.37
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为产物：
  描述：

  (20S)-3α,5-cyclo-20-formyl-6β-methoxy-5α-pregnane 在 吡啶 、 对甲苯磺酸 、 溶剂黄146 、 亚硝酰氯 、 sodium nitrite 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醇 、 水 、 异丙醇 、 苯 为溶剂， 反应 39.08h， 生成 3β-hydroxy-18a,18b-dihomoandrost-5-en-17,18a-dione
  参考文献：
  名称：

  Photoinduced molecular transformations. Part 132. A two-step intramolecular transposition of the 17β-acetyl group of pregnan-20-one to C-18 through the formation of cyclobutanols by the reaction of the excited carbonyl, followed by a selective β-scission of alkoxyl radicals generated from them

  摘要：

  New two-step transformations of a pregnan-20-one into 18-functionalized androstanes and 18a,18b-dihomoandrostanes are described; a type-II reaction of an excited pregnan-20-one protected in the A,B-ring gave the corresponding 20-hydroxy-18,20-cyclopregnane. Selective beta-scission of the cyclobutanoxyl radicals generated by irradiation of the nitrite or the hypoiodite gave a 5:4 ratio of the corresponding 18a,18b-dihomo-5-alpha-androstan-18a-one and 18-iodoandrostan-17-beta-yl acetate in 89% yield or 18a,18b-dihomo-5-alpha-androstane-17,18a-dione 17-oxime in 83% yield. The transformation involves a novel two-step intramolecular transposition of the 17-beta-acetyl group to C-18, and an oxygen insertion to the C-17-C-20 bond of pregnan-20-one.Several chemoselective transformations of the functional groups of the 18-iodoandrostan-17-one and 18a,18b-dihomo-5-alpha-pregnan-18a-one, including the synthesis of 3-beta-hydroxy-18a,18b-dihomoandrost-5-ene-17,18a-dione, are reported.

  DOI：

  10.1039/p19920001843

文献信息

• Photoinduced molecular transformations. Part 132. A two-step intramolecular transposition of the 17β-acetyl group of pregnan-20-one to C-18 through the formation of cyclobutanols by the reaction of the excited carbonyl, followed by a selective β-scission of alkoxyl radicals generated from them
  作者：Hiroshi Suginome、Yutaka Nakayama

  DOI：10.1039/p19920001843

  日期：——

  New two-step transformations of a pregnan-20-one into 18-functionalized androstanes and 18a,18b-dihomoandrostanes are described; a type-II reaction of an excited pregnan-20-one protected in the A,B-ring gave the corresponding 20-hydroxy-18,20-cyclopregnane. Selective beta-scission of the cyclobutanoxyl radicals generated by irradiation of the nitrite or the hypoiodite gave a 5:4 ratio of the corresponding 18a,18b-dihomo-5-alpha-androstan-18a-one and 18-iodoandrostan-17-beta-yl acetate in 89% yield or 18a,18b-dihomo-5-alpha-androstane-17,18a-dione 17-oxime in 83% yield. The transformation involves a novel two-step intramolecular transposition of the 17-beta-acetyl group to C-18, and an oxygen insertion to the C-17-C-20 bond of pregnan-20-one.Several chemoselective transformations of the functional groups of the 18-iodoandrostan-17-one and 18a,18b-dihomo-5-alpha-pregnan-18a-one, including the synthesis of 3-beta-hydroxy-18a,18b-dihomoandrost-5-ene-17,18a-dione, are reported.