5,17β-dihydroxy-4-nor-5α-androstan-2-one 17-acetate | 171485-22-6

• 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: 5,17β-dihydroxy-4-nor-5α-androstan-2-one 17-acetate
• 英文别名: [(3aR,3bS,5aS,6S,8aS,8bS,10aR)-10a-hydroxy-3a,5a-dimethyl-2-oxo-1,3,3b,4,5,6,7,8,8a,8b,9,10-dodecahydroindeno[5,4-e]inden-6-yl] acetate
• CAS: 171485-22-6
• 化学式: C₂₀H₃₀O₄
• 分子量: 334.456
• InChiKey: HVEKHSHVRVSXRD-ZYRLFZHTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  24
• 可旋转键数：
  2
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  63.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  5,17β-dihydroxy-4-nor-5α-androstan-2-one 17-acetate 在 4,4-二碘联苯 、 碘 作用下， 以 环己烷 为溶剂， 45.0 ℃ 、101.32 kPa 条件下， 反应 5.0h， 以17%的产率得到Acetic acid (E)-(3S,3aS,5aS,12aR,12bS)-3a,6-dimethyl-8,10-dioxo-1,2,3,3a,4,5,5a,8,9,10,11,12,12a,12b-tetradecahydro-cyclonona[e]inden-3-yl ester
  参考文献：
  名称：

  Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal .beta.-Peroxy Lactones

  摘要：

  A mild and efficient synthesis of beta-peroxy lactones by alkoxy radical beta-fragmentation reaction of gamma-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5 alpha-cholestan-2-one (1), 5-hydroxy-5 alpha-cholestan-2-one (2), and 5,17 beta-dihydroxy-4-nor-5 alpha-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I-2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by beta-fragmentation to yield the peroxy lactone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific beta-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal beta-peroxy lactones 8, 12, and 15 in moderate to good yields.

  DOI：

  10.1021/jo00130a020
• 作为产物：
  描述：

  17β-hydroxy-3α,5-epoxy-4-nor-5α-androstan-2-one acetate 在 sodium tetrahydroborate 、 二苯基二硒醚 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 0.17h， 以34%的产率得到A-nortestosterone acetate
  参考文献：
  名称：

  Tandem Carbon-Radical Peroxidation-Addition to Carbonyl Groups Reaction. A New Synthesis of Steroidal .beta.-Peroxy Lactones

  摘要：

  A mild and efficient synthesis of beta-peroxy lactones by alkoxy radical beta-fragmentation reaction of gamma-hydroxy carbonyl compounds is described. Steroidal models 5-hydroxy-4-nor-3-oxa-5 alpha-cholestan-2-one (1), 5-hydroxy-5 alpha-cholestan-2-one (2), and 5,17 beta-dihydroxy-4-nor-5 alpha-androstan-2-one 17-acetate (3) were synthesized to test the present methodology. These substrates are subjected to photolysis with visible light in the presence of (diacetoxyiodo)benzene, lead tetraacetate, or HgO, I-2, and molecular oxygen to generate the corresponding alkoxy radical. The fragmentation of this radical results in the carbon radical which is trapped by molecular oxygen in the key step to generate a peroxy radical. Intramolecular addition of this peroxy radical to the carbonyl group present in the molecule is followed by beta-fragmentation to yield the peroxy lactone radical. Subsequent trapping of this radical results in stable peroxy lactone. In all cases, regiospecific beta-fragmentations and stereoselective peroxidation at C-10 radical were observed. This operationally simple multistep radical procedure permitted us to synthesize steroidal beta-peroxy lactones 8, 12, and 15 in moderate to good yields.

  DOI：

  10.1021/jo00130a020

文献信息

• Sequential alkoxy radical fragmentation. A one-step method for breaking two 1,3-positioned CC bonds
  作者：Alicia Boto、Carmen Betancor、Rosendo Hernández、Mariá S. Rodríguez、Ernesto Suárez

  DOI：10.1016/s0040-4039(00)74111-6

  日期：1993.7

  Cyclic hydroxy-ketones (1) and (2) in the presence of (diacetoxyiodo)benzene or mercuric oxide and iodine under oxygen atmosphere and irradiation with visible light undergo a new sequential alkoxy radical fragmentation-radical peroxidation-peroxyradical cyclization-alkoxy radical fragmentation reaction. This methodology allows the cleavage of two 1,3-positioned C-C bonds in a single step and constitutes a new synthesis of beta-peroxylactones.