Cesium carbonate → 2-(4-Fluorophenyl)-6-(phenylsulfonyl)naphthalene

HRID 735304Notes

Reaction equation

HRID 735304 reaction equation
FC(F)(F)S(OC1C=C[C:14]2[C:9](=[CH:10][CH:11]=[C:12]([C:17]3[CH:22]=[CH:21][C:20]([F:23])=[CH:19][CH:18]=3)[CH:13]=2)C=1)(=O)=O.[C:26](=O)([O-])[O-].[Cs+].[Cs+].[C:32]1([S:38]([O-:40])=[O:39])[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.[Na+].[Cl-].[C:43]([NH3+])([CH3:46])([CH3:45])C>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C1(P(C2C=CC=CC=2)C2C3OC4C(=CC=CC=4P(C4C=CC=CC=4)C4C=CC=CC=4)C(C)(C)C=3C=CC=2)C=CC=CC=1.O>[F:23][C:20]1[CH:19]=[CH:18][C:17]([C:12]2[CH:11]=[CH:10][C:9]3[C:14](=[CH:26][CH:45]=[C:43]([S:38]([C:32]4[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=4)(=[O:40])=[O:39])[CH:46]=3)[CH:13]=2)=[CH:22][CH:21]=1

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 2723840Benzenesulfinic acid, sodium saltHCID 11355454t-Butylammonium chlorideHCID 866167346-(4-Fluorophenyl)-2-naphthyl trifluoromethanesulfonate

Product 1

HCID 115956862-(4-Fluorophenyl)-6-(phenylsulfonyl)naphthaleneYield 71%

Reagents, catalysts & solvents 4

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
120 °C

Procedure

A mixture of 6-(4-fluorophenyl)-2-naphthyl trifluoromethanesulfonate (Step 2, 260 mg, 0.7 mmol), cesium carbonate (345 mg, 1.06 mmol), sodium benzenesulfinate (140 mg, 0.85 mmol), tris(dibenzylideneacetone)dipalladium(0) (16 mg), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (20 mg) and tert-butylammonium chloride (235 mg, 0.84 mmol) in toluene (5 mL) was heated to 120° C. under nitrogen for 5 hours. The cooled reaction mixture was poured into water and extracted with ethyl acetate (x3). The combined organic layers were washed with water and brine, dried over MgSO4 and evaporated in vacuo. The residue was purified by flash column chromatography on silica, eluting with 20% ethyl acetate/isohexane, followed by trituration with 10% diethyl ether/isohexane to give the title compound as an off-white solid (180 mg, 71%). 1H NMR (500 MHz, CDCl3) δ 8.59 (1H, s), 8.05-7.95 (5H, m), 7.88 (1H, dd, J=1.8, 8.6 Hz), 7.81 (1H, dd, J=1.7, 8.5 Hz), 7.67-7.65 (2H, m), 7.57-7.49 (3H, m), 7.20-7.16 (2H, m).

Workup

  1. customThe cooled reaction mixture
  2. extractionextracted with ethyl acetate (x3)
  3. washThe combined organic layers were washed with water and brine
  4. dry with materialdried over MgSO4
  5. customevaporated in vacuo
  6. customThe residue was purified by flash column chromatography on silica
  7. washeluting with 20% ethyl acetate/isohexane

Sources & evidence

ORD record
ord-962628148e804959912a724e5adc8fe4
Source dataset
uspto-grants-2009_09
Patent number
US07592456B2

Reaction notes

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