Cesium carbonate → HCID 57586468, compound

HRID 420369Notes

Reaction equation

HRID 420369 reaction equation
Br[C:2]1[CH:3]=[C:4]([OH:9])[CH:5]=[C:6](Br)[CH:7]=1.B(O)(O)[C:11]1[CH:16]=[CH:15][C:14]2[O:17][CH2:18][O:19][C:13]=2[CH:12]=1.[S:22]1[CH:26]=[CH:25][C:24](B(O)O)=[CH:23]1.C(=O)([O-])[O-].[Cs+].[Cs+]>C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].C(COC)OC>[O:17]1[C:14]2[CH:15]=[CH:16][C:11]([C:2]3[CH:3]=[C:4]([OH:9])[CH:5]=[C:6]([C:24]4[CH:25]=[CH:26][S:22][CH:23]=4)[CH:7]=3)=[CH:12][C:13]=2[O:19][CH2:18]1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 122803,5-DibromophenolHCID 581760Thiophene-3-boronic acidHCID 2734371(2H-1,3-benzodioxol-5-yl)boronic acid

Product 1

HCID 57586468HCID 57586468, compoundYield 42.5%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 80711,2-DimethoxyethaneSolvent

Conditions

Temperature
97 °C

Procedure

To a mixture of 3,5-dibromophenol (59.54 mmol, 15 g), 3,4-(methylenedioxy) phenylboronic acid (77.40 mmol, 12.84 g), 3-thiopheneboronic acid (62.52 mmol, 8 g), PdCl2(dppf) (6.75 mmol, 4.94 g), and cesium carbonate (240 mmol, 78.19 g) was added dimethoxyethane (550 mL) at room temperature under nitrogen atmosphere. Then, the resulting light brown suspension was heated to 97° C. and stirred for 15 h. Then, the reaction mixture was cooled to room temperature and the solids were filtered-off and the cake was washed with ethyl acetate. The filtrate was diluted with water (300 mL) and the two layers were separated. The aqueous layer was extracted with ethyl acetate (2×100 mL) and the combined organic extracts were washed with brine solution (300 mL). The organic layer was dried over anhydrous magnesium sulfate and filtration of the drying agent and removal of the solvent gave the crude dark brown residue which was purified by two times using an ISCO (330 g) column chromatography eluting with 0-20% ethyl acetate in hexanes to afford the desired 3-benzo[1,3]dioxol-5-yl-5-thiophen-3-yl-phenol (7.48 g, 42.5%) as a white low melting solid. HRES(+) m/e calcd for C17H12O3S (M+H)+ 297.0580, found 297.0580

Workup

  1. temperatureThen, the reaction mixture was cooled to room temperature
  2. washthe cake was washed with ethyl acetate
  3. additionThe filtrate was diluted with water (300 mL)
  4. customthe two layers were separated
  5. extractionThe aqueous layer was extracted with ethyl acetate (2×100 mL)
  6. washthe combined organic extracts were washed with brine solution (300 mL)
  7. dry with materialThe organic layer was dried over anhydrous magnesium sulfate and filtration of the drying agent and removal of the solvent
  8. customgave the crude dark brown residue which
  9. customwas purified by two times
  10. washeluting with 0-20% ethyl acetate in hexanes

Sources & evidence

ORD record
ord-9d439cc9a379450ab9394f038afa3297
Source dataset
uspto-grants-2012_01
Patent number
US08093385B2

Reaction notes

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