Cesium carbonate → HCID 59275665, compound

HRID 1025067Notes

Reaction equation

HRID 1025067 reaction equation
C(=O)([O-])[O-].[Cs+].[Cs+].[F:7][C:8]1[CH:13]=[CH:12][C:11]([C:14]2[O:15][C:16]3[CH:27]=[C:26]([N+:28]([O-:30])=[O:29])[C:25](OS(C(F)(F)F)(=O)=O)=[CH:24][C:17]=3[C:18]=2[C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:10][CH:9]=1.[C:39]([O:43][C:44]([C:46]1[CH:47]=[C:48](B(O)O)[CH:49]=[CH:50][CH:51]=1)=[O:45])([CH3:42])([CH3:41])[CH3:40].O1CCOCC1>CCOC(C)=O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O>[C:39]([O:43][C:44]([C:46]1[CH:51]=[C:50]([C:25]2[C:26]([N+:28]([O-:30])=[O:29])=[CH:27][C:16]3[O:15][C:14]([C:11]4[CH:10]=[CH:9][C:8]([F:7])=[CH:13][CH:12]=4)=[C:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])[C:17]=3[CH:24]=2)[CH:49]=[CH:48][CH:47]=1)=[O:45])([CH3:42])([CH3:40])[CH3:41]

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 2773299(3-((Tert-butoxy)carbonyl)phenyl)boronic acidHCID 59275383HCID 59275383, compound

Product 1

HCID 59275665HCID 59275665, compoundYield 69.3%

Reagents, catalysts & solvents 3

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
90 °C

Procedure

Cesium carbonate (1.54 g, 4.71 mmol) was added to Pd(Ph3P)4 (182 mg, 0.157 mmol), ethyl 2-(4-fluorophenyl)-6-nitro-5-(trifluoromethylsulfonyloxy)benzofuran-3-carboxylate (1500 mg, 3.14 mmol), 3-(tert-butoxycarbonyl)phenylboronic acid (768 mg, 3.46 mmol). Dioxane (26 mL) and water (5 mL) was added at rt. The reaction was heated to 90° C. overnight. The reaction was allowed to cool was diluted with EtOAc and washed with sat NaHCO3, and sat NaCl. The organic phase was dried over Na2SO4, filtered and concentrated and purified on silica gel (Biotage, EtOAc/hexanes gradient, fraction collection at λ=254 nm) to give to give the titled compound (1.10 g, 69%). 1H NMR (300 MHz, DMSO-d6) δ ppm 8.60 (1 H, s), 8.08-8.18 (2 H, m), 8.02 (1 H, s), 7.95-8.01 (1 H, m), 7.88 (1 H, s), 7.58-7.70 (2 H, m), 7.46 (2 H, t, J=8.78 Hz), 4.34 (2 H, q, J=7.20 Hz), 1.56 (9 H, s), 1.27 (3 H, t, J=7.14 Hz). LC-MS retention time: 2.13 min; m/z (MH+): parent does not ionize. LC data was recorded on a Shimadzu LC-10AS liquid chromatograph equipped with a Waters XBridge 5 u C18 4.6×50 mm column using a SPD-10AV UV-Vis detector at a detector wave length of 220 nM. The elution conditions employed a flow rate of 5 ml/min, a gradient of 100% solvent A/0% solvent B to 0% solvent A/100% solvent B, a gradient time of 2 min, a hold time of 1 min, and an analysis time of 3 min where solvent A was 5% acetonitrile/95% H2O/10 mM ammonium acetate and solvent B was 5% H2O/95% acetonitrile/10 mM ammonium acetate. MS data was determined using a Micromass Platform for LC in electrospray mode.

Workup

  1. temperatureto cool
  2. washwashed
  3. dry with materialThe organic phase was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated
  6. custompurified on silica gel (Biotage, EtOAc/hexanes gradient, fraction collection at λ=254 nm)
  7. customto give

Sources & evidence

ORD record
ord-eb1ad683780b497a87c49aa95a9c3ade
Source dataset
uspto-grants-2014_05
Patent number
US08722688B2

Reaction notes

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