Cesium carbonate → HCID 58423790, compound

HRID 1408840Notes

Reaction equation

HRID 1408840 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:20](=[CH:21][CH:22]=1)[O:19][C:7]1([CH2:12][CH2:11][CH:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[CH2:9][CH2:8]1)[CH2:6][C:5]2=[O:23].[C:24]([C:26]1[CH:27]=[C:28](B(O)O)[CH:29]=[CH:30][CH:31]=1)#[N:25].C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[O:23]=[C:5]1[C:4]2[C:20](=[CH:21][CH:22]=[C:2]([C:30]3[CH:31]=[C:26]([CH:27]=[CH:28][CH:29]=3)[C:24]#[N:25])[CH:3]=2)[O:19][C:7]2([CH2:12][CH2:11][CH:10]([C:13]3[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=3)[CH2:9][CH2:8]2)[CH2:6]1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27343253-Cyanophenylboronic acidHCID 58424815HCID 58424815, compound

Product 1

HCID 58423790HCID 58423790, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 218864351,4-Dioxane--water (1/1)Solvent

Conditions

Temperature
95 °C

Procedure

In a 50 mL round bottom flask was placed 6-bromo-4′-phenylspiro[chroman-2,1′-cyclohexan]-4-one (300 mg, 0.811 mmol), 3-cyanobenzeneboronic acid (155 mg, 1.06 mmol), PdCl2(PPh3)2 (57 mg, 0.08 mmol) and cesium carbonate (661 mg, 2.03 mmol). This solid mixture was dissolved in a Dioxane/water mixture (8 mL, 6:1 ratio, respectively). The solution was purged with a N2 stream for 30 seconds. A condenser was attached to the flask and the reaction was allowed to stir at 95° C. for 1 hour. At this time, the mixture was filtered through a Celite plug. The plug was rinsed with dichloromethane (20 mL) and water (20 mL). The phases in the filtrate were separated. The aqueous phase was back-extracted with dichloromethane twice (5 mL/each). The combined organic phases were dried over MgSO4, filtered and concentrated under reduce pressure. The crude material was purified by flash chromatography (ISCO, 12 g SiO2 cartridge, ethyl acetate/hexanes as the eluents). The corresponding fractions were combined and concentrated under reduce pressure yielding 3-(4-oxo-4′-phenylspiro[chroman-2,1′-cyclohexane]-6-yl)benzonitrile (173 mg, 0.440 mmol, 58% yield) as a light yellow oil.

Workup

  1. customIn a 50 mL round bottom flask was placed
  2. customThe solution was purged with a N2 stream for 30 seconds
  3. customA condenser was attached to the flask
  4. filtrationAt this time, the mixture was filtered through a Celite plug
  5. washThe plug was rinsed with dichloromethane (20 mL) and water (20 mL)
  6. customThe phases in the filtrate were separated
  7. extractionThe aqueous phase was back-extracted with dichloromethane twice (5 mL/each)
  8. dry with materialThe combined organic phases were dried over MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated
  11. customThe crude material was purified by flash chromatography (ISCO, 12 g SiO2 cartridge, ethyl acetate/hexanes as the eluents)
  12. concentrationconcentrated

Sources & evidence

ORD record
ord-a25901c6bbe245ff939f278a66beb0af
Source dataset
uspto-grants-2014_12
Patent number
US08921359B2

Reaction notes

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