(E)-trimethyl(2-(tributylstannyl)vinyl)silane → HCID 70497062, compound

HRID 244310Notes

Reaction equation

HRID 244310 reaction equation
[NH2:1][C:2]1[N:7]=[C:6]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=2[F:15])[N:5]=[C:4]([C:16]([O:18][CH3:19])=[O:17])[C:3]=1I.[CH3:21][Si:22]([CH3:39])([CH3:38])/[CH:23]=[CH:24]/[Sn](CCCC)(CCCC)CCCC>O1CCOCC1.C(OCC)(=O)C.O.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:1][C:2]1[N:7]=[C:6]([C:8]2[CH:13]=[CH:12][C:11]([Cl:14])=[CH:10][C:9]=2[F:15])[N:5]=[C:4]([C:16]([O:18][CH3:19])=[O:17])[C:3]=1/[CH:24]=[CH:23]/[Si:22]([CH3:39])([CH3:38])[CH3:21]

Participants

7

Reactant 2

HCID 10949136(E)-trimethyl(2-(tributylstannyl)vinyl)silaneHCID 70498054HCID 70498054, compound

Product 1

HCID 70497062HCID 70497062, compoundYield 76%

Reagents, catalysts & solvents 4

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

Methyl 6-amino-2-(4-chloro-2-fluorophenyl)-5-iodopyrimidine-4-carboxylate (400 mg, 0.981 mmol) and tetrakis(triphenylphosphine)palladium(0) (113 mg, 0.098 mmol) were added to a 20 mL Biotage microwave reaction vessel. The vessel was sealed and purged with nitrogen gas. (E)-trimethyl(2-(tributylstannyl)vinyl)silane (497 mg, 1.276 mmol) in dioxane (4907 μl) was added and the reaction mixture was stirred overnight at 90° C. under nitrogen. The cooled reaction mixture was diluted with ethyl acetate and water. The organic phase was washed with saturated sodium chloride, dried over magnesium sulfate, filtered, and concentrated onto silica. Purification by flash chromatography (SiO2, 0-20% EtOAc:Hex gradient) provided the title compound as a tan solid (0.283 g, 76% yield): 1H NMR (400 MHz, DMSO-d6) d 0.16 (s, 9H), 3.78 (s, 3H), 6.14 (d, J=19.1 Hz, 1H), 6.80 (d, J=19.1 Hz, 1H), 7.21-7.68 (m, 4H), 7.92 (t, J=8.4 Hz, 1H); 19F NMR (376 MHz, DMSO-d6) d −110.46; ESIMS m/z 380 ([M+H]+), 378 ([M−H]−).

Workup

  1. customThe vessel was sealed
  2. custompurged with nitrogen gas
  3. customThe cooled reaction mixture
  4. washThe organic phase was washed with saturated sodium chloride
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated onto silica
  8. customPurification by flash chromatography (SiO2, 0-20% EtOAc:Hex gradient)

Sources & evidence

ORD record
ord-92936842f8304821817b8657abbbd4da
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

Loading…