Cesium carbonate → HCID 58229492, compound

HRID 1963796Notes

Reaction equation

HRID 1963796 reaction equation
[Cl:1][C:2]1[C:7]([NH:8][S:9]([C:12]2[CH:17]=[CH:16][C:15]([F:18])=[CH:14][CH:13]=2)(=[O:11])=[O:10])=[CH:6][C:5](B2OC(C)(C)C(C)(C)O2)=[CH:4][N:3]=1.Br[C:29]1[CH:34]=[CH:33][C:32]2[O:35][CH2:36][CH2:37][O:38][C:31]=2[CH:30]=1.C(=O)([O-])[O-].[Cs+].[Cs+].O1CCOCC1>[NH4+].[Cl-].[Pd+2].ClC1C=C[C-](P(C2C=CC=CC=2)C2C=CC=CC=2)C=1Cl.[C-]1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=C1.[Fe+2].O>[Cl:1][C:2]1[C:7]([NH:8][S:9]([C:12]2[CH:13]=[CH:14][C:15]([F:18])=[CH:16][CH:17]=2)(=[O:10])=[O:11])=[CH:6][C:5]([C:29]2[CH:34]=[CH:33][C:32]3[O:35][CH2:36][CH2:37][O:38][C:31]=3[CH:30]=2)=[CH:4][N:3]=1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 1041416-Bromo-1,4-benzodioxaneHCID 53363355n-[2-Chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-yl]-4-fluorobenzene-1-sulfonamide

Product 1

HCID 58229492HCID 58229492, compoundYield 81%

Reagents, catalysts & solvents 3

HCID 178478230HCID 178478230, compoundCatalystHCID 962WaterSolventHCID 25517Ammonium ChlorideSolvent

Conditions

Temperature
100 °C

Procedure

To a 50 mL round-bottomed flask was added N-(2-chloro-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-3-yl)-4-fluorobenzenesulfonamide (62 mg, 150 μmol), 1-bromo-3,4-(ethylenedioxy)benzene (32 mg, 150 μmol, Aldrich, St. Louis, Mo.), dichloro 1,1′-bis(diphenylphosphino)ferrocene palladium (II) (12 mg, 15 μmol), Cesium carbonate (98 mg, 300 μmol), dioxane (1 mL), water (0.2 mL). The reaction mixture was stirred at 100° C. for 1 h. The mixture was cooled down to room temperature. The reaction mixture was diluted with saturated NH4Cl (5 mL) and extracted with EtOAc (2×30 mL). The organic extract was washed with saturated NaCl (10 mL), dried over Na2SO4, filtered and concentrated in vacuo and the residue was purified by silica gel chromatography, eluting with 30% EtOAc/hexanes to give N-(2-chloro-5-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)pyridin-3-yl)-4-fluorobenzenesulfonamide (51 mg, 81% yield). MS (EI, pos.) calcd for C19H14ClFN2O4S: 420.0; found 420.9. 1H NMR (300 MHz, CHLOROFORM-d) δ ppm 4.32 (s, 4 H) 6.88-7.09 (m, 4 H) 7.09-7.21 (m, 2 H) 7.74-7.87 (m, 2 H) 8.12 (d, J=2.19 Hz, 1 H) 8.30 (d, J=2.34 Hz, 1 H).

Workup

  1. temperatureThe mixture was cooled down to room temperature
  2. extractionextracted with EtOAc (2×30 mL)
  3. extractionThe organic extract
  4. washwas washed with saturated NaCl (10 mL)
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customthe residue was purified by silica gel chromatography
  9. washeluting with 30% EtOAc/hexanes

Sources & evidence

ORD record
ord-c12b1a4b99994cb09ae59bdcb05f90dc
Source dataset
uspto-grants-2013_04
Patent number
US08415376B2

Reaction notes

Loading…