17aβ-(t-Butoxy)-3-methoxy-D-homo-9,10-secooestra-1,3,5(10),8(14)-tetraen-6,9-dion | 65083-12-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 17aβ-(t-Butoxy)-3-methoxy-D-homo-9,10-secooestra-1,3,5(10),8(14)-tetraen-6,9-dion
• CAS: 65083-12-7
• 化学式: C₂₄H₃₂O₄
• 分子量: 384.516
• InChiKey: PTSWIVLNVMOFIE-UPVQGACJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  17aβ-(t-Butoxy)-3-methoxy-D-homo-9,10-secooestra-1,3,5(10),8(14)-tetraen-6,9-dion 在 palladium on activated charcoal chromium(VI) oxide 、 高氯酸 、 硫酸 、 氢气 、 溶剂黄146 作用下， 生成 3-methoxy-13β-D-homoestra-1,3,5(10)-trien-17a-one
  参考文献：
  名称：

  [（+）-D-高雌酮3-甲基醚的全合成（作者翻译）]。

  摘要：

  Total Synthesis of (+)‐D‐Homoestrone 3‐methyl etherA novel total synthesis of (+)‐D‐homoestrone 3‐methyl ether (21) is described starting from (S)‐8a‐methyl‐3,4,8,8a‐tetrahydro‐2H, 7H‐naphthalene‐1,6‐dione (1) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m‐methoxyphenacyl bromide (4) as an AB‐building block to give the dioxo‐secosteroid 5. Hydrogenation of 5 affords the trans‐decalone 11. As by‐products the epimeric cis‐decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ9(11)‐tetraene 14. Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21. It was found that 14 and also the derived Δ8‐isomer 15a add hydrogen from the α‐face of the molecule to an extent of about 80%. The 8α‐D‐homoestrone derivatives 20a and 23 as well as the 9β‐isomers 19a and 22 were characterized.

  DOI：

  10.1002/hlca.19770600717
• 作为产物：
  描述：

  (4aS,5S)-4,4a,5,6,7,8-hexahydro-5-hydroxy-4a-methylnaphthalen-2(3H)-one 在 磷酸 、 三氟化硼乙醚 作用下， 生成 17aβ-(t-Butoxy)-3-methoxy-D-homo-9,10-secooestra-1,3,5(10),8(14)-tetraen-6,9-dion
  参考文献：
  名称：

  [（+）-D-高雌酮3-甲基醚的全合成（作者翻译）]。

  摘要：

  Total Synthesis of (+)‐D‐Homoestrone 3‐methyl etherA novel total synthesis of (+)‐D‐homoestrone 3‐methyl ether (21) is described starting from (S)‐8a‐methyl‐3,4,8,8a‐tetrahydro‐2H, 7H‐naphthalene‐1,6‐dione (1) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m‐methoxyphenacyl bromide (4) as an AB‐building block to give the dioxo‐secosteroid 5. Hydrogenation of 5 affords the trans‐decalone 11. As by‐products the epimeric cis‐decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ9(11)‐tetraene 14. Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21. It was found that 14 and also the derived Δ8‐isomer 15a add hydrogen from the α‐face of the molecule to an extent of about 80%. The 8α‐D‐homoestrone derivatives 20a and 23 as well as the 9β‐isomers 19a and 22 were characterized.

  DOI：

  10.1002/hlca.19770600717

文献信息

• Totalsynthese von (+)-<i>D</i>-Homoöstron-3-methyläther
  作者：Jürg Gutzwiller、Werner Meier、Andor Fürst

  DOI：10.1002/hlca.19770600717

  日期：1977.11.2

  Total Synthesis of (+)‐D‐Homoestrone 3‐methyl etherA novel total synthesis of (+)‐D‐homoestrone 3‐methyl ether (21) is described starting from (S)‐8a‐methyl‐3,4,8,8a‐tetrahydro‐2H, 7H‐naphthalene‐1,6‐dione (1) as a chiral synthon for the rings C and D. The key step involves alkylation of the derived 3 with m‐methoxyphenacyl bromide (4) as an AB‐building block to give the dioxo‐secosteroid 5. Hydrogenation of 5 affords the trans‐decalone 11. As by‐products the epimeric cis‐decalones 12 and 13 were characterized. Cyclization of 11 leads under kinetic control predominantly to the Δ9(11)‐tetraene 14. Catalytic hydrogenation of 14 and subsequent modification in ring D give the title compound 21. It was found that 14 and also the derived Δ8‐isomer 15a add hydrogen from the α‐face of the molecule to an extent of about 80%. The 8α‐D‐homoestrone derivatives 20a and 23 as well as the 9β‐isomers 19a and 22 were characterized.