(E)-trimethyl(2-(tributylstannyl)vinyl)silane → HCID 70497312, compound

HRID 244324Notes

Reaction equation

HRID 244324 reaction equation
[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH3:10])[N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[C:3]=1I.[CH3:16][Si:17]([CH3:34])([CH3:33])/[CH:18]=[CH:19]/[Sn](CCCC)(CCCC)CCCC>ClC(Cl)C.C(OCC)(=O)C.O.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>[NH2:1][C:2]1[C:7]([F:8])=[C:6]([CH2:9][CH3:10])[N:5]=[C:4]([C:11]([O:13][CH3:14])=[O:12])[C:3]=1/[CH:19]=[CH:18]/[Si:17]([CH3:34])([CH3:33])[CH3:16]

Participants

7

Reactant 2

HCID 10949136(E)-trimethyl(2-(tributylstannyl)vinyl)silaneHCID 70498014HCID 70498014, compound

Product 1

HCID 70497312HCID 70497312, compoundYield 57.9%

Reagents, catalysts & solvents 4

HCID 178418476HCID 178418476, compoundCatalystHCID 962WaterSolventHCID 63651,1-DichloroethaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
120 °C

Procedure

Methyl 4-amino-6-ethyl-5-fluoro-3-iodopicolinate (270 mg, 0.833 mmol) and bis(triphenylphosphine)palladium(II) dichloride (58.5 mg, 0.083 mmol) were combined in a microwave reactor vessel. (E)-trimethyl(2-(tributylstannyl)vinyl)silane (649 mg, 1.666 mmol) dissolved in dichloroethane (0.8 mL) was added and the reaction mixture was heated at 120° C. for 30 min a microwave reactor. The cooled reaction mixture was diluted with ethyl acetate and water. The aqueous phase was extracted three more times with ethyl acetate. The combined organic phases were dried over magnesium sulfate, filtered, and concentrated on to silica. The product was purifed by flash chromatography (SiO2, 0-30% EtOAc:Hex gradient) to provide the title compound as an off-white solid (143 mg, 0.482 mmol, 57.9% yield): 1H NMR (400 MHz, DMSO-d6) δ 0.14 (s, 9H), 1.16 (t, J=7.6 Hz, 3H), 2.65 (qd, J=7.6, 2.6 Hz, 2H), 3.71 (s, 3H), 5.99 (d, J=19.3 Hz, 1H), 6.25 (s, 2H), 6.84 (d, J=19.2 Hz, 1H); 19F NMR (376 MHz, DMSO-d6) δ −148.85; ESIMS m/z 297 ([M+H]+), 295 ([M−H]−).

Workup

  1. additionwas added
  2. customThe cooled reaction mixture
  3. extractionThe aqueous phase was extracted three more times with ethyl acetate
  4. dry with materialThe combined organic phases were dried over magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated on to silica

Sources & evidence

ORD record
ord-c6d86f7d929145bda0b755c5d16f712e
Source dataset
uspto-grants-2014_02
Patent number
US08658568B2

Reaction notes

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