Dichloromethane → HCID 68183135, compound

HRID 1615529Notes

Reaction equation

HRID 1615529 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.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.O1CCOCC1>[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 4

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

Product 1

HCID 68183135HCID 68183135, compound

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

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), 1,1′-bis(diphenylphosphino)ferrocenepalladium(II) dichloride, dichloromethane (96 mg, 0.12 mmol) and 1,4-dioxane (30 mL). 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 then diluted with EtOAc (100 mL). The mixture was transferred to a separatory funnel and washed with water (50 mL×2). The combined aqueous phases were extracted with EtOAc (50 mL×2). The combined organic phases were dried over anhydrous MgSO4. Insoluble materials were removed by filtration and the filtrate was concentrated under reduced pressure. The residue was purified using column chromatography on silica gel (40 g RediSep column, gradient 30% EA in hexane to 100% EA in hexane) to give the product (420 mg; 77%) as a colorless crystalline solid: 1H NMR (400 MHz, CDCl3) δ 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. customThe mixture was transferred to a separatory funnel
  4. washwashed with water (50 mL×2)
  5. extractionThe combined aqueous phases were extracted with EtOAc (50 mL×2)
  6. dry with materialThe combined organic phases were dried over anhydrous MgSO4
  7. customInsoluble materials were removed by filtration
  8. concentrationthe filtrate was concentrated under reduced pressure
  9. customThe residue was purified
  10. customto give the product (420 mg; 77%) as a colorless crystalline solid

Sources & evidence

ORD record
ord-340f9174b4a04cbc8d9cc10a6870dc2a
Source dataset
uspto-grants-2014_07
Patent number
US08765746B2

Reaction notes

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