Dimethylformamide → Dimethyl 2'-fluoro-5'-(methyloxy)-1,1'-biphenyl-2,4-dicarboxylate

HRID 2098915Notes

Reaction equation

HRID 2098915 reaction equation
FC(F)(F)S(O[C:7]1[CH:16]=[CH:15][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:9][C:8]=1[C:17]([O:19][CH3:20])=[O:18])(=O)=O.CN(C=O)C.[F:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][C:30]=1B(O)O.C(=O)([O-])[O-].[K+].[K+]>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>[F:28][C:29]1[CH:34]=[CH:33][C:32]([O:35][CH3:36])=[CH:31][C:30]=1[C:7]1[C:8]([C:17]([O:19][CH3:20])=[O:18])=[CH:9][C:10]([C:11]([O:13][CH3:14])=[O:12])=[CH:15][CH:16]=1

Participants

7

Reactant 4

HCID 6228DimethylformamideHCID 11430Potassium CarbonateHCID 41572112-Fluoro-5-methoxyphenylboronic acidHCID 120175464-[[(Trifluoromethyl)sulfonyl]oxy]-1,3-benzenedicarboxylic acid dimethyl ester

Product 1

HCID 57706522Dimethyl 2'-fluoro-5'-(methyloxy)-1,1'-biphenyl-2,4-dicarboxylate

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

To a stirred solution of dimethyl 4-(trifluoromethylsulfonyloxy)isophthalate T9.2 (39.00 g, 114 mmol) in DMF (228 mL, 114 mmol) at 23° C. was added 2-fluoro-5-methoxyphenylboronic acid (29 g, 171 mmol) (commercially available from Aldrich), potassium carbonate (47 g, 342 mmol), followed by tetrakis(triphenylphosphine)palladium (9.2 g, 8.0 mmol). The mixture was heated to 90° C. and stirring was continued for 18 hours. The reaction was cooled to room temperature. Water was added to the reaction, and the resulting mixture was extracted with EtOAc. The organic layer was dried over MgSO4 and concentrated. The residue was purified by silica gel flash chromatography (0-20% EtOAc/hexane) to afford dimethyl 2′-fluoro-5′-(methyloxy)-1,1′-biphenyl-2,4-dicarboxylate T9.3 as a clear oil (32.00 g, 88% yield). MS ESI (pos.) m/e: 319.1 (M+H)+.

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. extractionthe resulting mixture was extracted with EtOAc
  3. dry with materialThe organic layer was dried over MgSO4
  4. concentrationconcentrated
  5. customThe residue was purified by silica gel flash chromatography (0-20% EtOAc/hexane)

Sources & evidence

ORD record
ord-c5cca4185fd84fd5bf463f3f2cd61dd9
Source dataset
uspto-grants-2013_05
Patent number
US08450522B2

Reaction notes

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