Acetic Acid → (1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid

HRID 2405478

反応式

HRID 2405478 の反応式
[CH3:1][O:2][C:3]([C:5]1[CH:10]=[CH:9][C:8]([C:11]2[C:12]([CH3:49])([CH3:48])[C@H:13]3[C@:26]([CH3:29])([CH2:27][CH:28]=2)[C@@H:25]2[C@:16]([CH3:47])([C@@:17]4([CH3:46])[C@H:22]([CH2:23][CH2:24]2)[C@H:21]2[C@H:30]([C:33]([CH3:35])=[CH2:34])[CH2:31][CH2:32][C@:20]2([C:36]([O:38]CC2C=CC=CC=2)=[O:37])[CH2:19][CH2:18]4)[CH2:15][CH2:14]3)=[CH:7][CH:6]=1)=[O:4].C(O)(=O)C>C(O)C.O1CCOCC1.[Pd]>[CH:33]([C@H:30]1[C@@H:21]2[C@@H:22]3[C@@:17]([CH3:46])([CH2:18][CH2:19][C@@:20]2([C:36]([OH:38])=[O:37])[CH2:32][CH2:31]1)[C@@:16]1([CH3:47])[C@@H:25]([C@:26]2([CH3:29])[C@@H:13]([CH2:14][CH2:15]1)[C:12]([CH3:49])([CH3:48])[C@@H:11]([C:8]1[CH:7]=[CH:6][C:5]([C:3]([O:2][CH3:1])=[O:4])=[CH:10][CH:9]=1)[CH2:28][CH2:27]2)[CH2:24][CH2:23]3)([CH3:35])[CH3:34]

参加物

6

反応物 2

HCID 176Acetic AcidHCID 67776728(1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR 13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate

生成物 1

HCID 67775516(1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid収率 100%

試薬・触媒・溶媒 3

HCID 23938Palladium触媒HCID 702Ethanol溶媒HCID 312751,4-Dioxane溶媒

実験手順

To a solution of (1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-benzyl 9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysene-3a-carboxylate (0.2 g, 0.302 mmol) in ethanol (5 mL), 1,4-dioxane (7 mL), and acetic acid (0.5 mL, 8.73 mmol) was added Pd/C (10% by wt.) (0.1 g, 0.094 mmol). The mixture was flushed with N2 and was put on the Parr shaker under 30 psi H2. After 2 h, the reaction was checked by 1H NMR. The benzyl group had been removed, but the alkene still remained. The mixture was again flushed with N2. An additional 50 mg of 10% Pd/C was added and the mixture was pressurized to 40 psi H2. After stirring the mixture overnight, it reaction was removed from the Parr shaker and the palladium catalyst was removed by filtration. The filtrate was concentrated under reduced pressure to give the expected product, (1S,3aS,5aR,5bR,7aS,9S,11aS,11bR,13aR,13bR)-1-isopropyl-9-(4-(methoxycarbonyl)phenyl)-5a,5b,8,8,11a-pentamethylicosahydro-1H-cyclopenta[a]chrysene-3a-carboxylic acid (0.174 g, 100% yield), as a white solid. 1H NMR (500 MHz, CHLOROFORM-d) δ ppm 7.91 (d, J=8.24 Hz, 2H), 7.22 (d, J=8.55 Hz, 2H), 3.89 (s, 3H), 2.39 (dd, J=13.12, 3.05 Hz, 1H), 2.19-2.29 (m, 3H), 2.01-2.13 (m, 1H), 0.99 (s, 3H), 0.96 (s, 3H), 0.95 (s, 3H), 0.86 (d, J=6.71 Hz, 3H), 0.79-1.92 (m, 22H), 0.76 (d, J=6.71 Hz, 3H), 0.75 (s, 3H), 0.68 (s, 3H).

後処理

  1. customThe mixture was flushed with N2
  2. customThe benzyl group had been removed
  3. customThe mixture was again flushed with N2
  4. additionAn additional 50 mg of 10% Pd/C was added
  5. customthe mixture overnight, it reaction
  6. customwas removed from the Parr shaker
  7. customthe palladium catalyst was removed by filtration
  8. concentrationThe filtrate was concentrated under reduced pressure

出典と根拠

ORDレコード
ord-cd4f46976fef4658b02d11706bd6a979
出典データセット
uspto-grants-2014_08
特許番号
US08802661B2

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