Dichloromethane → HCID 68183135, compound

HRID 1615482Notes

Reaction equation

HRID 1615482 reaction equation
Br[C:2]1[S:3][C:4]2[CH2:10][CH2:9][C:8]([CH3:12])([CH3:11])[C:7](=[O:13])[C:5]=2[CH:6]=1.[N:14]1[CH:19]=[CH:18][C:17](B(O)O)=[CH:16][CH:15]=1.ClCCl.O1CCOCC1.C(=O)([O-])[O-].[Cs+].[Cs+]>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].O>[CH3:11][C:8]1([CH3:12])[C:7](=[O:13])[C:5]2[CH:6]=[C:2]([C:17]3[CH:18]=[CH:19][N:14]=[CH:15][CH:16]=3)[S:3][C:4]=2[CH2:10][CH2:9]1

Participants

9

Reactant 5

HCID 6344DichloromethaneHCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 2734379(Pyridin-4-yl)boronic acidHCID 68183065HCID 68183065, compound

Product 1

HCID 68183135HCID 68183135, compoundYield 77.7%

Reagents, catalysts & solvents 3

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

In a 100 ml round bottomed flask, were placed 2-bromo-5,5-dimethyl-6,7-dihydro-1-benzothiophen-4(5H)-one (550 mg, 2.1 mmol), pyridine-4-boronic acid (326 mg, 2.65 mmol) and 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) dichloride, dichloromethane (96 mg, 0.12 mmol) and then suspended in 1,4-dioxane (30 mL, 400 mmol). To the mixture were added cesium carbonate (3.08 g, 9.45 mmol) and water (20 mL). The mixture was stirred for 16 h at 120° C. The mixture was allowed to cool to rt and then diluted with EtOAc (100 mL), which was washed with water (50 mL×2). The combined aqueous phase was extracted with EtOAc (50 mL×2). The combined organic phase was dried over anhydrous MgSO4. Insoluble materials were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified by pre-packed silica gel (40 g) column chromatography eluted with a 30% to 100% EtOAc/hexane to obtain title compound (420 mg, 77%) as a colorless crystalline solid. LCMS: (FA) ES+ 258; 1H NMR (400 MHz, d-chloroform) δ ppm 8.60 (dd, 2H), 7.77 (s, 1H), 7.43 (dd, 2H), 3.09 (t, 2H), 2.10 (t, 2H), 1.24 (s, 6H).

Workup

  1. customIn a 100 ml round bottomed flask, were placed
  2. temperatureto cool to rt
  3. washwas washed with water (50 mL×2)
  4. extractionThe combined aqueous phase was extracted with EtOAc (50 mL×2)
  5. dry with materialThe combined organic phase was dried over anhydrous MgSO4
  6. customInsoluble materials were removed by filtration
  7. concentrationthe filtrate was concentrated under reduced pressure
  8. customThe residue was purified by pre-packed silica gel (40 g) column chromatography
  9. washeluted with a 30% to 100% EtOAc/hexane

Sources & evidence

ORD record
ord-5d8fbab23a6d4fdca422bc306c7d4fd9
Source dataset
uspto-grants-2014_07
Patent number
US08765746B2

Reaction notes

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