Potassium Carbonate → HCID 86676414, compound

HRID 405051Notes

Reaction equation

HRID 405051 reaction equation
[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

Participants

10

Reactant 5

HCID 11430Potassium CarbonateHCID 62657Potassium Phosphate, TribasicHCID 2735133Sodium Carbonate Monohydrate2×HCID 2773301(4-((Tert-butoxy)carbonyl)phenyl)boronic acidHCID 86666260HCID 86666260, compound

Product 1

HCID 86676414HCID 86676414, compoundYield 92.6%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 3776IsopropanolSolventHCID 312751,4-DioxaneSolvent

Procedure

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.

Workup

  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

Sources & evidence

ORD record
ord-eba058fa70be47bb8c3a0ecd1f5c57f8
Source dataset
uspto-grants-2014_06
Patent number
US08748415B2

Reaction notes

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