(E)-trimethyl(2-(tributylstannyl)vinyl)silane → HCID 70497566, compound

HRID 244323Notes

Reaction equation

HRID 244323 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[C:11]([F:16])[CH:10]=2)[N:5]=[C:4]([C:17]([O:19][CH3:20])=[O:18])[C:3]=1I.[CH3:22][Si:23]([CH3:40])([CH3:39])/[CH:24]=[CH:25]/[Sn](CCCC)(CCCC)CCCC>O1CCOCC1.C(OCC)(=O)C>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([C:9]2[CH:14]=[CH:13][C:12]([Cl:15])=[C:11]([F:16])[CH:10]=2)[N:5]=[C:4]([C:17]([O:19][CH3:20])=[O:18])[C:3]=1/[CH:25]=[CH:24]/[Si:23]([CH3:40])([CH3:39])[CH3:22]

Participants

5

Reactant 2

HCID 10949136(E)-trimethyl(2-(tributylstannyl)vinyl)silaneHCID 70497132Methyl 4-amino-6-(4-chloro-3-fluorophenyl)-5-fluoro-3-iodopicolinate

Product 1

HCID 70497566HCID 70497566, compoundYield 79.5%

Reagents, catalysts & solvents 2

HCID 8857Ethyl AcetateSolvent2×HCID 312751,4-DioxaneSolvent

Conditions

Temperature
120 °C

Procedure

Methyl 4-amino-6-(4-chloro-3-fluorophenyl)-5-fluoro-3-iodopicolinate (350 mg, 0.824 mmol), and tetrakis triphenylphosphine palladium(0) (95 mg, 0.082 mmol) were combined in a Biotage microwave reaction vessel that was then sealed and purged with nitrogen. (E)-trimethyl(2-(tributylstannyl)vinyl)silane (417 mg, 1.072 mmol) in dioxane (4122 μl) was added and the reaction mixture was heated in a microwave reactor at 120° C. for 30 min The cooled reaction mixture was diluted with ethyl acetate and washed with saturated sodium chloride. The organic phase was dried over magnesium sulfate, filtered and concentrated on to silica. The product was purified by flash chromatography. (SiO2, 0-20% EtOAc:Hex gradient) to provide the title compound as a tan solid (260 mg, 0.655 mmol, 79% yield); 1H NMR (400 MHz, DMSO-d6) d 0.17 (s, 9H), 3.76 (s, 3H), 6.09 (d, J=19.2 Hz, 1H), 6.60 (s, 2H), 6.91 (d, J=19.2 Hz, 1H), 7.75 (dd, J=3.8, 1.9 Hz, 2H), 7.83 (dd, J=10.8, 1.3 Hz, 1H); 19F NMR (376 MHz, DMSO-d6) d −145.16 , −115.98; ESIMS m/z 398 ([M+H]+).

Workup

  1. customwas then sealed
  2. custompurged with nitrogen
  3. customThe cooled reaction mixture
  4. washwashed with saturated sodium chloride
  5. dry with materialThe organic phase was dried over magnesium sulfate
  6. filtrationfiltered
  7. concentrationconcentrated on to silica
  8. customThe product was purified by flash chromatography

Sources & evidence

ORD record
ord-89294aff165f489099d7c1f0130fd73f
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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