Water → HCID 89649709, compound

HRID 2175939Notes

Reaction equation

HRID 2175939 reaction equation
[CH3:1][C:2]1[C:3](B2OC(C)(C)C(C)(C)O2)=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6].Cl[C:22]1[N:27]=[CH:26][CH:25]=[CH:24][N:23]=1.C([O-])([O-])=O.[Na+].[Na+].O>CC1OCCC1.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]>[CH3:1][C:2]1[C:3]([C:22]2[N:27]=[CH:26][CH:25]=[CH:24][N:23]=2)=[C:4]([CH:9]=[CH:10][CH:11]=1)[C:5]([O:7][CH3:8])=[O:6]

Participants

7

Reactant 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 744042-ChloropyrimidineHCID 67170476HCID 67170476, compound

Product 1

HCID 89649709HCID 89649709, compoundYield 23%

Reagents, catalysts & solvents 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)Catalyst2×HCID 73012-MethyltetrahydrofuranSolvent

Conditions

Temperature
150 °C

Procedure

In a microwave vial was dissolved methyl 3-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate (619 mg, 2.24 mmol) and 2-chloropyrimidine (314 mg, 2.69 mmol) in 2-MeTHF (10 mL). Na2CO3 (713 mg, 6.73 mmol) was then added followed by water (3.4 mL) and the reaction mixture was degassed with N2 for 45 minutes. Pd(dppf)Cl2 (66 mg, 0.09 mmol) and the reaction mixture was heated at 75° C. for 28 h. More Pd(dppf)Cl2 (33 mg, 0.045 mmol) was added and the reaction mixture was heated at 150° C. for 3.5 h. The mixture was filtered through a pad of celite and rinsed with EtOAc and water. The layers were separated and the aqueous was extracted once with EtOAc. The combined organic layers were dried over MgSO4, filtered and evaporated. The crude was purified via silica gel chromatography (0-50% EtOAc in hexanes) to afford the title compound (116 mg, 23%). MS (ESI) mass calcd. for C13H12N2O2, 228.1; m/z found 229.1 [M+H]+. 1H NMR (500 MHz, CDCl3) 8.95-8.76 (m, 2H), 7.99-7.75 (m, 1H), 7.50-7.44 (m, 1H), 7.43-7.37 (m, 1H), 7.32-7.24 (m, 1H), 3.64 (s, 3H), 2.15 (s, 3H).

Workup

  1. customthe reaction mixture was degassed with N2 for 45 minutes
  2. filtrationThe mixture was filtered through a pad of celite
  3. washrinsed with EtOAc and water
  4. customThe layers were separated
  5. extractionthe aqueous was extracted once with EtOAc
  6. dry with materialThe combined organic layers were dried over MgSO4
  7. filtrationfiltered
  8. customevaporated
  9. customThe crude was purified via silica gel chromatography (0-50% EtOAc in hexanes)

Sources & evidence

ORD record
ord-9316b26a06e2404aa4a77ddd4aa7025a
Source dataset
uspto-grants-2015_06
Patent number
US09062078B2

Reaction notes

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