(3R,3aS,5aS,5bS,7aS,9S,11aS,11bS,12aS,12bS)-9-Hydroxy-3,11a-dimethyl-octadecahydro-2-oxa-benzo[a]cyclopenta[i]fluoren-12-one | 78425-59-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并吡喃类
• 英文名称: (3R,3aS,5aS,5bS,7aS,9S,11aS,11bS,12aS,12bS)-9-Hydroxy-3,11a-dimethyl-octadecahydro-2-oxa-benzo[a]cyclopenta[i]fluoren-12-one
• CAS: 78425-59-9
• 化学式: C₂₁H₃₂O₃
• 分子量: 332.483
• InChiKey: BMHLYXUCJSLGGU-NXLPQBFTSA-N

反应信息

• 作为反应物：
  描述：

  (3R,3aS,5aS,5bS,7aS,9S,11aS,11bS,12aS,12bS)-9-Hydroxy-3,11a-dimethyl-octadecahydro-2-oxa-benzo[a]cyclopenta[i]fluoren-12-one 在 chromium(VI) oxide 作用下， 以 吡啶 为溶剂， 反应 5.0h， 生成 (3R,3aS,5aS,5bS,7aS,11aS,11bS,12aS,12bS)-3,11a-Dimethyl-hexadecahydro-2-oxa-benzo[a]cyclopenta[i]fluorene-9,12-dione
  参考文献：
  名称：

  The Transformation of Jervine into 18-FunctionalD-Homo-C-norsteroids. IV. The Transformation of Jervine into (20R)-18,20β-Epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-Acetatevia(20R)-18,20β-Epoxy-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-Acetate

  摘要：

  Catalytic hydrogenation of (22S,25S)-N-acetyl-3β,23β-dihydroxyveratra-5,13(17)-dien-11-one 3-acetate over rhodium-platinum catalyst in acetic acid gave (22S,25S)-N-acetyl-3β,23β-dihydroxyveratranin-11 -one 3-acetate (2) in ca 70% yield, together with two minor products. Irradiation of 2 in benzene containing mercury(II) oxide and iodine gave 20-formyl-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (5) in 43% yield, accompanied by the 17-epimer of (22S,23R,25S)-N-acetyl-3β-hydroxy-5α-jervanin-11-one 3-acetate (4%). Aldehyde 5 was transformed into 3β-hydroxy-12α,17β-ethyletiojervane-11,20-dione 3-acetate (15) (79% yield) by photo- or coppercatalysed oxygenation of the corresponding enamine. Reduction of 15 with sodium borohydride gave 3β,20β-dihydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (17) as a major product (69%), together with the 20-epimer. The hypoiodite reaction of 17 gave 18,20β-epoxy-3β-hydroxy-17β-ethyl-12α-etiojervan-11-one 3-acetate (19) in 92% yield. Hydrolysis of 19 resulted in the isomerization of the C/D ring junction to give 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-11 -one (20), the first 18-functional C/D trans  D-homo-C-norsteroid ever prepared. Wolff-Kishner reduction of 20 gave the corresponding 11-deoxo compound; its acetylation followed by oxidation yielded 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-acetate. The 11-oxo function of 19 can be reduced quite easily with lithium aluminum hydride to give the corresponding 11β-ol.

  DOI：

  10.1246/bcsj.54.852
• 作为产物：
  描述：

  3β-hydroxy-12α,17β-ethyletiojervane-11,20-dione 3-acetate 在 氢氧化钾 、 sodium tetrahydroborate 、 碘 、 mercury(II) oxide 作用下， 以 乙醇 、 氯仿 、 水 、 乙酸乙酯 、 苯 为溶剂， 反应 8.0h， 生成 (3R,3aS,5aS,5bS,7aS,9S,11aS,11bS,12aS,12bS)-9-Hydroxy-3,11a-dimethyl-octadecahydro-2-oxa-benzo[a]cyclopenta[i]fluoren-12-one
  参考文献：
  名称：

  The Transformation of Jervine into 18-FunctionalD-Homo-C-norsteroids. IV. The Transformation of Jervine into (20R)-18,20β-Epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-Acetatevia(20R)-18,20β-Epoxy-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-Acetate

  摘要：

  Catalytic hydrogenation of (22S,25S)-N-acetyl-3β,23β-dihydroxyveratra-5,13(17)-dien-11-one 3-acetate over rhodium-platinum catalyst in acetic acid gave (22S,25S)-N-acetyl-3β,23β-dihydroxyveratranin-11 -one 3-acetate (2) in ca 70% yield, together with two minor products. Irradiation of 2 in benzene containing mercury(II) oxide and iodine gave 20-formyl-3β-hydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (5) in 43% yield, accompanied by the 17-epimer of (22S,23R,25S)-N-acetyl-3β-hydroxy-5α-jervanin-11-one 3-acetate (4%). Aldehyde 5 was transformed into 3β-hydroxy-12α,17β-ethyletiojervane-11,20-dione 3-acetate (15) (79% yield) by photo- or coppercatalysed oxygenation of the corresponding enamine. Reduction of 15 with sodium borohydride gave 3β,20β-dihydroxy-12α,17β-ethyletiojervan-11-one 3-acetate (17) as a major product (69%), together with the 20-epimer. The hypoiodite reaction of 17 gave 18,20β-epoxy-3β-hydroxy-17β-ethyl-12α-etiojervan-11-one 3-acetate (19) in 92% yield. Hydrolysis of 19 resulted in the isomerization of the C/D ring junction to give 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-11 -one (20), the first 18-functional C/D trans  D-homo-C-norsteroid ever prepared. Wolff-Kishner reduction of 20 gave the corresponding 11-deoxo compound; its acetylation followed by oxidation yielded 18,20β-epoxy-3β-hydroxy-17β-ethyletiojervan-18-one 3-acetate. The 11-oxo function of 19 can be reduced quite easily with lithium aluminum hydride to give the corresponding 11β-ol.

  DOI：

  10.1246/bcsj.54.852