Tri-tert-butylphosphine tetrafluoroborate → HCID 57541263, compound

HRID 421739Notes

Reaction equation

HRID 421739 reaction equation
CC(C)([O-])C.[Na+].[CH3:7][N:8]([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[S:9]([CH2:12][C:13]([O:15][CH3:16])=[O:14])(=[O:11])=[O:10].Br[C:24]1[CH:25]=[CH:26][C:27]2[CH:38]=[CH:37][C:31]3=[N:32][CH:33]=[C:34]([Cl:36])[CH:35]=[C:30]3[C:29](=[O:39])[C:28]=2[CH:40]=1.F[B-](F)(F)F.C([PH+](C(C)(C)C)C(C)(C)C)(C)(C)C>C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O1CCOCC1>[Cl:36][C:34]1[CH:35]=[C:30]2[C:29](=[O:39])[C:28]3[CH:40]=[C:24]([CH:12]([S:9]([N:8]([CH3:7])[C:17]4[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=4)(=[O:10])=[O:11])[C:13]([O:15][CH3:16])=[O:14])[CH:25]=[CH:26][C:27]=3[CH:38]=[CH:37][C:31]2=[N:32][CH:33]=1

Participants

7

Reactant 4

HCID 2734635Tri-tert-butylphosphine tetrafluoroborateHCID 14002850HCID 14002850, compoundHCID 159808187-Bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-B]pyridin-5-oneHCID 23676156Sodium t-butoxide

Product 1

HCID 57541263HCID 57541263, compound

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

Sodium tert-butoxide (8.99 g, 94 mmol) was added in one portion to a 250 mL flask containing methyl {[methyl(phenyl)amino]sulfonyl}acetate (7.59 g, 31.2 mmol) and dioxane (125 ml) at room temperature. After 15 min., 7-bromo-3-chloro-5H-benzo[4,5]cyclohepta[1,2-b]pyridin-5-one (10.00 g, 31.2 mmol) was added followed by palladium(II) acetate (0.350 g, 1.560 mmol) and tri-t-butylphosphonium tetrafluoroborate (1.358 g, 4.68 mmol). The resulting suspension was degassed by sparging with nitrogen for 30 min. Then, the mixture was heated to 90° C. in a pre-warmed bath and left to stir for 1 h. Then, the reaction mixture was cooled to room temperature, acidified with 1N HCl (100 mL), basified with saturated aqueous sodium hydrogen carbonate (400 mL) and extracted with dichloromethane (3×250 mL). The combined organics were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient) to afford the title compound as a yellow foam. 1H NMR (600 MHz, DMSO-D6) δ 8.99 (d, 1H); 8.46 (d, 1H); 8.42 (d, 1H); 8.03 (dd, 1H); 7.81 (d, 1H); 7.44 (d, 1H); 7.33 (d, 1H); 7.22 (m, 2H); 7.17 (m, 2H); 7.11 (m, 1H); 6.10 (s, 1H); 3.71 (s, 3H); 3.20 (s, 3H). LRMS (APCI) calculated for C24H20ClN2O5S [M+H]+, 483.1; found 483.0.

Workup

  1. customThe resulting suspension was degassed
  2. customby sparging with nitrogen for 30 min
  3. waitleft
  4. temperatureThen, the reaction mixture was cooled to room temperature
  5. extractionextracted with dichloromethane (3×250 mL)
  6. dry with materialThe combined organics were dried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by column chromatography on silica gel (EtOAc/Hexanes gradient)

Sources & evidence

ORD record
ord-844eb02a2d244076b595c0d02a87bfa7
Source dataset
uspto-grants-2012_01
Patent number
US08101603B2

Reaction notes

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