Cesium carbonate → 5-bromo-2-ethenylpyrimidine

HRID 1399982Notes

Reaction equation

HRID 1399982 reaction equation
[Br:1][C:2]1[CH:3]=[N:4][C:5](I)=[N:6][CH:7]=1.[CH3:9][C:10]1(C)C(C)(C)OB(C=C)O1.C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.O.CCOC(C)=O.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:3]=[N:4][C:5]([CH:9]=[CH2:10])=[N:6][CH:7]=1

Participants

8

Reactant 3

HCID 10796Cesium carbonateHCID 52330122-Ethenyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70066515-Bromo-2-iodopyrimidine

Product 1

HCID 536286645-bromo-2-ethenylpyrimidine

Reagents, catalysts & solvents 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

5-Bromo-2-iodo-pyrimidine (2.15 g, 7.55 mmol), 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborolane (1.60 mL, 9.43 mmol) and PdCl2(dppf). (300 mg, 0.40 mmol) were dissolved in 1,4-dioxane (15 mL). A solution of Cs2CO3 (4.91 g, 15.1 mmol) in H2O (5 mL) was added and the mixture heated at 80° C. for 30 min. The reaction mixture was diluted with EtOAc (100 mL), washed with H2O, brine and separated. The organic fraction was dried and concentrated in vacuo. Purification by chromatography on silica, eluting with 5-25% EtOAc/heptane gave i (1.10 g, 79%). MS 185.11 & 187.09 [M+H]+.

Workup

  1. washwashed with H2O, brine
  2. customseparated
  3. customThe organic fraction was dried
  4. concentrationconcentrated in vacuo
  5. customPurification by chromatography on silica
  6. washeluting with 5-25% EtOAc/heptane
  7. customgave i (1.10 g, 79%)

Sources & evidence

ORD record
ord-a621bf537cc34e7ea4b946af5ebe7a3b
Source dataset
uspto-grants-2014_12
Patent number
US08906902B2

Reaction notes

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