Potassium Carbonate → tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-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]chrysen-9-yl)benzoate

HRID 405051ノート

反応式

HRID 405051 の反応式
[C:1]([O:9][CH2:10][C@:11]12[CH2:44][CH2:43][C@@H:42]([C:45]([CH3:47])=[CH2:46])[C@@H:12]1[C@@H:13]1[C@@:26]([CH3:29])([CH2:27][CH2:28]2)[C@@:25]2([CH3:30])[C@@H:16]([C@:17]3([CH3:41])[C@@H:22]([CH2:23][CH2:24]2)[C:21]([CH3:32])([CH3:31])[C:20](OS(C(F)(F)F)(=O)=O)=[CH:19][CH2:18]3)[CH2:15][CH2:14]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.O.C(=O)([O-])[O-].[Na+].[Na+].[C:55]([O:59][C:60]([C:62]1[CH:67]=[CH:66][C:65](B(O)O)=[CH:64][CH:63]=1)=[O:61])([CH3:58])([CH3:57])[CH3:56].C(=O)([O-])[O-].[K+].[K+].P([O-])([O-])([O-])=O.[K+].[K+].[K+]>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.CC(O)C>[C:1]([O:9][CH2:10][C@:11]12[CH2:44][CH2:43][C@@H:42]([C:45]([CH3:47])=[CH2:46])[C@@H:12]1[C@@H:13]1[C@@:26]([CH3:29])([CH2:27][CH2:28]2)[C@@:25]2([CH3:30])[C@@H:16]([C@:17]3([CH3:41])[C@@H:22]([CH2:23][CH2:24]2)[C:21]([CH3:31])([CH3:32])[C:20]([C:65]2[CH:66]=[CH:67][C:62]([C:60]([O:59][C:55]([CH3:58])([CH3:57])[CH3:56])=[O:61])=[CH:63][CH:64]=2)=[CH:19][CH2:18]3)[CH2:15][CH2:14]1)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

参加物

10

反応物 5

HCID 11430Potassium CarbonateHCID 62657Potassium Phosphate, TribasicHCID 2735133Sodium Carbonate Monohydrate2 回HCID 2773301(4-((Tert-butoxy)carbonyl)phenyl)boronic acidHCID 86666260((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate

生成物 1

HCID 86676414tert-butyl 4-((1R,3aS,5aR,5bR,7aR,11aS,11bR,13aR,13bR)-3a-(benzoyloxymethyl)-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]chrysen-9-yl)benzoate収率 92.6%

試薬・触媒・溶媒 4

HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 3776Isopropanol溶媒HCID 312751,4-Dioxane溶媒

実験手順

To a solution of ((1R,3aS,5aR,5bR,7aR,11aR,11bR,13aR,13bR)-5a,5b,8,8,11a-pentamethyl-1-(prop-1-en-2-yl)-9-(trifluoromethylsulfonyloxy)-2,3,3a,4,5,5a,5b,6,7,7a,8,11,11a,11b,12,13,13a,13b-octadecahydro-1H-cyclopenta[a]chrysen-3a-yl)methyl benzoate (9.85 g, 14.55 mmol) in 1,4-dioxane (50 ml) was added 2-propanol (50.0 ml), water (20 ml), sodium carbonate monohydrate (5.41 g, 43.7 mmol), 4-tert-butoxycarbonylphenylboronic acid (4.85 g, 21.83 mmol), and tetrakis(triphenylphosphine)palladium(0) (0.504 g, 0.437 mmol). Potassium carbonate and potassium phosphate can also be used instead of sodium carbonate monohydrate. The sides of the flask were rinsed with an additional 20 ml of dioxane and the mixture was attached to a reflux condenser, was flushed with N2 and was heated to reflux. Upon heating, the solids in the mixture dissolved completely. The solution was heated at reflux for 3.5 h, was cooled to rt and was diluted with 200 ml of water. The mixture was extracted with ethyl acetate (3×150 ml) and the combined organic layers were dried with Na2SO4. The drying agent was removed by filtration and the filtrate was concentrated under reduced pressure. The residue purified by flash chromatography using a 0-15% EtOAc in hexanes gradient to afford the title compound as a white foam (9.5 g, ˜83% pure based on 1H NMR integrations). The product was used in the next step with no additional purification.

後処理

  1. washThe sides of the flask were rinsed with an additional 20 ml of dioxane
  2. customthe mixture was attached to a reflux condenser
  3. customwas flushed with N2
  4. temperaturewas heated to reflux
  5. temperatureUpon heating
  6. dissolutionthe solids in the mixture dissolved completely
  7. temperatureThe solution was heated
  8. temperatureat reflux for 3.5 h
  9. additionwas diluted with 200 ml of water
  10. extractionThe mixture was extracted with ethyl acetate (3×150 ml)
  11. dry with materialthe combined organic layers were dried with Na2SO4
  12. customThe drying agent was removed by filtration
  13. concentrationthe filtrate was concentrated under reduced pressure
  14. customThe residue purified by flash chromatography

出典と根拠

ORDレコード
ord-eba058fa70be47bb8c3a0ecd1f5c57f8
出典データセット
uspto-grants-2014_06
特許番号
US08748415B2

反応ノート

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