Tributylvinyltin → 5-Ethenyl-4-fluoropyridin-2-amine

HRID 69146Notes

Reaction equation

HRID 69146 reaction equation
Cl.Br[C:3]1[C:4]([F:10])=[CH:5][C:6]([NH2:9])=[N:7][CH:8]=1.[CH2:11]([Sn](CCCC)(CCCC)C=C)[CH2:12]CC>O1CCOCC1.CCOC(C)=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[F:10][C:4]1[C:3]([CH:11]=[CH2:12])=[CH:8][N:7]=[C:6]([NH2:9])[CH:5]=1

Participants

6

Reactant 2

HCID 81998Tributylvinyltin2×HCID 716270675-Bromo-4-fluoropyridin-2-amine hydrochloride

Product 1

HCID 552838425-Ethenyl-4-fluoropyridin-2-amine

Reagents, catalysts & solvents 3

HCID 11979704Tetrakis(triphenylphosphine)palladiumCatalyst2×HCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

5-Bromo-4-fluoro-pyridin-2-ylamine mono HCl salt (xvii) (368 mg, 1.62 mmol), tributyl(vinyl)stannane (0.52 mL, 1.78 mmol) and palladium tetrakis(triphenylphosphine) (19 mg, 0.016 mmol) in dioxane (6 mL) under argon were heated under microwave irradiation at 120° C. for 45 min. Were then added tributyl(vinyl)stannane (0.2 mL, 0.685 mmol) and palladium tetrakis(triphenylphosphine) (7 mg, 0.006 mmol) and the RM was placed under argon and heated once more under microwave irradiation at 120° C. for 45 min. The RM was diluted with EtOAc and washed with brine, dried over Na2SO4, filtered and evaporated to dryness. The residue was purified by chromatography with hexane and EtOAc to yield the title product as a yellow solid (tR 1.76 min (conditions 8), MH+=139).

Workup

  1. washwashed with brine
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered
  4. customevaporated to dryness
  5. customThe residue was purified by chromatography with hexane and EtOAc

Sources & evidence

ORD record
ord-90a5a3ec9c8743f2b363a98f2d86c93a
Source dataset
uspto-grants-2014_09
Patent number
US08822468B2

Reaction notes

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