Dichloromethane → HCID 59280078, compound

HRID 1518118Notes

Reaction equation

HRID 1518118 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][C:9]([F:12])([F:11])[F:10])[C:3]=1I.[NH2:14][C:15]1[CH:20]=[CH:19][C:18](B2OC(C)(C)C(C)(C)O2)=[CH:17][C:16]=1[N+:30]([O-:32])=[O:31].C(Cl)Cl>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]>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[C:4]([O:8][C:9]([F:12])([F:11])[F:10])[C:3]=1[C:18]1[CH:19]=[CH:20][C:15]([NH2:14])=[C:16]([N+:30]([O-:32])=[O:31])[CH:17]=1

Participants

5

Reactant 3

HCID 6344DichloromethaneHCID 162179142-Nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 59842432HCID 59842432, compound

Product 1

HCID 59280078HCID 59280078, compoundYield 87%

Reagents, catalysts & solvents 1

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

Conditions

Temperature
90 °C

Procedure

2-Fluoro-1-iodo-6-trifluoromethoxybenzene (612 mg, 2.00 mmol, prepared as described in WO2005/097136), 4-amino-3-nitrophenylboronic acid pinacol ester (1.3 eq., 687 mg, 2.60 mmol), and (dppf)PdCl2.DCM (0.05 eq., 81.6 mg, 0.100 mmol) were placed in a 40 mL vial equipped with a magnetic stir bar. The vial was evacuated and backflushed with Ar, and DME (10 mL) and 2M aq Na2 CO3 (4 mL) were added via syringe. The vial was capped tightly and placed in a heating block where the reaction was stirred at 90° C. for 24 h. The reaction was cooled to room temperature, diluted with EtOAc, and washed sequentially with water and brine. The organic extract was dried over anhydrous MgSO4, filtered, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using an 80-g SiO2 pre-packed column eluting with EtOAc/hexanes, 0:1 to 2:3, v/v over 30 min, yielding 548 mg (87%) of the desired compound. 1H-NMR (400 MHz, CDCl3) δ: 8.21 (s, 1H), 7.30-7.47 (m, 2H), 7.18 (d, J=8.1 Hz, 1H), 7.14 (t, J=8.6 Hz, 1H), 6.91 (d, J=6.6 Hz, 1H), 5.37 (br. s., 2H).

Workup

  1. customvial equipped with a magnetic stir bar
  2. customThe vial was evacuated
  3. additionCO3 (4 mL) were added via syringe
  4. customThe vial was capped tightly
  5. temperatureThe reaction was cooled to room temperature
  6. additiondiluted with EtOAc
  7. washwashed sequentially with water and brine
  8. extractionThe organic extract
  9. dry with materialwas dried over anhydrous MgSO4
  10. filtrationfiltered
  11. customthe solvent was removed under reduced pressure
  12. customThe crude product was purified by column chromatography
  13. washeluting with EtOAc/hexanes, 0:1 to 2:3, v/v over 30 min

Sources & evidence

ORD record
ord-3005ba15dda94d7ba0bc4deeb3694192
Source dataset
uspto-grants-2012_07
Patent number
US08232409B2

Reaction notes

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