Cesium carbonate → HCID 89464042, compound

HRID 706782Notes

Reaction equation

HRID 706782 reaction equation
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([F:27])=[C:6]([S:8]([NH:11][C:12]2[CH:17]=[CH:16][C:15](B3OC(C)(C)C(C)(C)O3)=[CH:14][CH:13]=2)(=[O:10])=[O:9])[CH:7]=1.[Cl:28][C:29]1[C:30]([C:36]#[N:37])=[N:31][CH:32]=[C:33](Cl)[N:34]=1.C(=O)([O-])[O-].[Cs+].[Cs+].O1CCOCC1>[Pd](Cl)Cl.C1(P(C2C=CC=CC=2)[C-]2C=CC=C2)C=CC=CC=1.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([F:27])=[C:6]([S:8]([NH:11][C:12]2[CH:13]=[CH:14][C:15]([C:33]3[CH:32]=[N:31][C:30]([C:36]#[N:37])=[C:29]([Cl:28])[N:34]=3)=[CH:16][CH:17]=2)(=[O:9])=[O:10])[CH:7]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 529877443,5-Dichloropyrazine-2-carbonitrileHCID 89463765HCID 89463765, compound

Product 1

HCID 89464042HCID 89464042, compound

Reagents, catalysts & solvents 2

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

Conditions

Temperature
100 °C

Procedure

5-Chloro-2-fluoro-N-[4-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-phenyl]-benzenesulfonamide (709 mg) was added to a reaction vessel containing a magnetic stirring bar together with 3,5-dichloro-pyrazine-2-carbonitrile (300 mg), 1,1′-bis(diphenylphosphino)ferrocene-palladium(II) dichloride (Pd(dppf)2Cl2) (100 mg) and cesium carbonate (1.69 g), followed by 6 ml dioxane and 1 ml water, and the mixture heated to 100° C. under stirring. After 3 h the reaction mixture was cooled to RT and quenched with a saturated aqueous sodium bicarbonate solution (40 ml) and extracted with EtOAc (3×80 ml). The combined aqueous phases were dried over sodium sulfate, filtered and evaporated to afford the crude product as a brown oil. Purification by flash chromatography on silica gel using a mixture of EtOAc and heptane as the eluent afforded 5-chloro-N-[4-(6-chloro-5-cyano-pyrazin-2-yl)-phenyl]-2-fluoro-benzenesulfonamide as a brown foam after evaporation of the solvents under reduced pressure. Yield: 160 mg (22%).

Workup

  1. temperatureAfter 3 h the reaction mixture was cooled to RT
  2. customquenched with a saturated aqueous sodium bicarbonate solution (40 ml)
  3. extractionextracted with EtOAc (3×80 ml)
  4. dry with materialThe combined aqueous phases were dried over sodium sulfate
  5. filtrationfiltered
  6. customevaporated
  7. customto afford the crude product as a brown oil
  8. customPurification by flash chromatography on silica gel using
  9. additiona mixture of EtOAc and heptane as the eluent

Sources & evidence

ORD record
ord-b4c2c2575bbb41e69b5b6cef0d394987
Source dataset
uspto-grants-2015_11
Patent number
US09174993B2

Reaction notes

Loading…