Cesium carbonate → HCID 67043864, compound

HRID 1503380Notes

Reaction equation

HRID 1503380 reaction equation
Br[C:2]1[CH:10]=[C:9]2[C:5]([CH2:6][C:7]3([CH2:15][CH:14]([O:16][CH3:17])[CH:13]([O:18][CH3:19])[CH2:12]3)[C:8]2=[O:11])=[CH:4][CH:3]=1.[C:20]([C:22]1[CH:23]=[C:24](B(O)O)[CH:25]=[CH:26][CH:27]=1)#[N:21].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>[CH3:19][O:18][CH:13]1[CH:14]([O:16][CH3:17])[CH2:15][C:7]2([CH2:6][C:5]3[C:9](=[CH:10][C:2]([C:26]4[CH:27]=[C:22]([CH:23]=[CH:24][CH:25]=4)[C:20]#[N:21])=[CH:3][CH:4]=3)[C:8]2=[O:11])[CH2:12]1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27343253-Cyanophenylboronic acidHCID 66584748HCID 66584748, compound

Product 1

HCID 67043864HCID 67043864, compoundYield 97%

Reagents, catalysts & solvents 2

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

Conditions

Temperature
110 °C

Procedure

In a microwave vial was placed 6′-bromo-3,4-dimethoxyspiro[cyclopentane-1,2′-inden]-1′(3′H)-one 1st isomer (23 mg, 0.071 mmol), 3-cyanobenzeneboronic acid (14 mg, 0.095 mmol), PdCl2(PPh3)2 (5 mg, 0.007 mmol) and cesium carbonate (58 mg, 0.178 mmol). This solid mixture was dissolved in a Dioxane/water mixture (1.0 mL, 6:1 ratio, respectively). The solution was purged with a N2 stream for 30 seconds. The vessel was placed in the microwave and heated to 110° C. for 30 minutes. After that time, the mixture was filtered through a Celite plug. The plug was rinsed with dichloromethane (2 mL) and water (2 mL). The phases in the filtrate were separated. The aqueous phase was back-extracted with dichloromethane (2 mL). The combined organic phases were washed with brine, 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-(3,4-dimethoxy-1′-oxo-1′,3′-dihydrospiro[cyclopentane-1,2′-indene]-6′-yl)benzonitrile 2nd isomer (24 mg, 0.069 mmol, 97% yield).

Workup

  1. customThe solution was purged with a N2 stream for 30 seconds
  2. filtrationAfter that time, the mixture was filtered through a Celite plug
  3. washThe plug was rinsed with dichloromethane (2 mL) and water (2 mL)
  4. customThe phases in the filtrate were separated
  5. extractionThe aqueous phase was back-extracted with dichloromethane (2 mL)
  6. washThe combined organic phases were washed with brine
  7. dry with materialdried over MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customThe crude material was purified by flash chromatography (ISCO, 12 g SiO2 cartridge, ethyl acetate/hexanes as the eluents)
  11. concentrationconcentrated

Sources & evidence

ORD record
ord-922b943b28664712bfb5b7a4f76da08f
Source dataset
uspto-grants-2015_12
Patent number
US09212153B2

Reaction notes

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