Potassium Carbonate → HCID 56602322, compound

HRID 514043Notes

Reaction equation

HRID 514043 reaction equation
[Br:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[C:5]([CH3:27])[C:6]([C:20](=[O:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])=[C:7]2OS(C(F)(F)F)(=O)=O.[Cl:28][C:29]1[CH:34]=[CH:33][C:32](B(O)O)=[CH:31][CH:30]=1.C(=O)([O-])[O-].[K+].[K+]>C1(C)C=CC=CC=1.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]>[Br:1][C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[C:5]([CH3:27])[C:6]([C:20](=[O:26])[C:21]([O:23][CH2:24][CH3:25])=[O:22])=[C:7]2[C:32]1[CH:33]=[CH:34][C:29]([Cl:28])=[CH:30][CH:31]=1

Participants

6

Reactant 3

HCID 11430Potassium CarbonateHCID 742994-Chlorophenylboronic acidHCID 86691543HCID 86691543, compound

Product 1

HCID 56602322HCID 56602322, compoundYield 60.6%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 1140TolueneSolvent

Procedure

To a solution of ethyl 2-(5-bromo-3-methyl-1-(trifluoromethylsulfonyloxy)naphthalen-2-yl)-2-oxoacetate (1.2 g, 2.56 mmol) and 4-chlorophenylboronic acid (440 mg, 2.81 mmol) in toluene was added 2 M potassium carbonate (2.8 mL, 5.63 mmol) and PdCl2(dppf) (187 mg, 0.256 mmol) and the reaction was degassed with argon 10 minutes. The reaction was stirred at room temperature for 4 hours. The reaction was filtered, diluted with water, extracted with ethyl acetate and concentrated. The crude reaction was purified by flash column chromatography (silica gel, ethyl acetate/hexanes) followed by reverse phase HPLC (Gemini, 40-100% ACN/H2O+0.1% TFA). Product was lyophilized to give 670 mg of ethyl 2-(5-bromo-1-(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-oxoacetate (36A) as a yellow oil, 1H-NMR: 400 MHz, (CDCl3) δ: 8.20 (s, 1H), 8.13 (d, J=8.8 Hz, 1H), 7.85 (d, J=6.8 Hz, 1H), 7.68 (t, J=7.2 Hz, 1H), 7.51 (d, J=8.8 Hz, 2H), 7.39 (d, J=8.4 Hz, 2H), 3.95 (q, J=6.8 Hz, 2H), 2.41 (s, 3H), 1.14 (t, J=7.2 Hz, 5H); and 109 mg of ethyl 2-(1,5-bis(4-chlorophenyl)-3-methylnaphthalen-2-yl)-2-oxoacetate (36B) as a white solid. 1H-NMR: 400 MHz, (CDCl3) δ: 7.72 (s, 1H), 7.59-7.56 (m, 1H), 7.50 (t, J=8.0 Hz, 2H), 7.46-7.44 (m, 5H), 7.43 (d, J=2.4 Hz, 1H), 7.28 (d, J=8.0 Hz, 2H), 3.94 (q, J=7.2 Hz, 2H), 2.42 (s, 3H), 1.14 (t, J=7.2 Hz, 3H).

Workup

  1. customthe reaction was degassed with argon 10 minutes
  2. filtrationThe reaction was filtered
  3. additiondiluted with water
  4. extractionextracted with ethyl acetate
  5. concentrationconcentrated
  6. customThe crude reaction
  7. customwas purified by flash column chromatography (silica gel, ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-45e2e7d700cf4be38d0b7af20dd109a7
Source dataset
uspto-grants-2015_08
Patent number
US09102614B2

Reaction notes

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