Cesium carbonate → 5-Fluoro-4-vinylpyrimidine

HRID 1051194Notes

Reaction equation

HRID 1051194 reaction equation
Br[C:2]1[C:7]([F:8])=[CH:6][N:5]=[CH:4][N:3]=1.[CH:9]([B-](F)(F)F)=[CH2:10].[K+].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C([O-])([O-])=O.[Cs+].[Cs+]>CC1CCCO1.O.C(OC)(C)(C)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1>[F:8][C:7]1[C:2]([CH:9]=[CH2:10])=[N:3][CH:4]=[N:5][CH:6]=1

Participants

9

Reactant 4

HCID 10796Cesium carbonateHCID 11776TriphenylphosphineHCID 23679353Potassium vinyltrifluoroborateHCID 448285354-Bromo-5-fluoropyrimidine

Product 1

HCID 736728815-Fluoro-4-vinylpyrimidineYield 41%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 73012-MethyltetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
75 °C

Procedure

4-Bromo-5-fluoropyrimidine (5 g) was reacted with potassium vinyltrifluorborate (1.05 equivalents) in the presence of (PPh3)2PdCl2 (0.02 eq), PPh3 (0.02 eq), and Cs2CO3 (3 equivalents) in a mixture of methyl tetrahydrofuran (85 ml) and water (8.5 ml). The reaction was heated at 75° C. for about 5.5 hours. The reaction mixture was then diluted with methyl tert-butyl ether (50 ml), followed by aqueous extraction. The crude product was purified by distillation at 170 mbar (90-110° C.). The product was obtained as a colourless oil (1.44 g, 41% yield).

Workup

  1. extractionfollowed by aqueous extraction
  2. distillationThe crude product was purified by distillation at 170 mbar (90-110° C.)

Sources & evidence

ORD record
ord-c9839f38f65c466cb5669f69415e8c12
Source dataset
uspto-grants-2016_07
Patent number
US09388167B2

Reaction notes

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