Tributylvinyltin → 6-chloro-1-(tetrahydro-pyran-2-yl)-3-vinyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylic acid ethyl ester

HRID 82033Notes

Reaction equation

HRID 82033 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15](I)=[N:14][N:13]([CH:17]3[CH2:22][CH2:21][CH2:20][CH2:19][O:18]3)[C:8]=2[N:9]=[C:10]([Cl:12])[CH:11]=1)=[O:5])[CH3:2].[CH2:23]([Sn](CCCC)(CCCC)C=C)[CH2:24]CC>O1CCCC1.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>[CH2:1]([O:3][C:4]([C:6]1[C:7]2[C:15]([CH:23]=[CH2:24])=[N:14][N:13]([CH:17]3[CH2:22][CH2:21][CH2:20][CH2:19][O:18]3)[C:8]=2[N:9]=[C:10]([Cl:12])[CH:11]=1)=[O:5])[CH3:2]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 86678158HCID 86678158, compound

Product 1

HCID 866781686-chloro-1-(tetrahydro-pyran-2-yl)-3-vinyl-1H-pyrazolo[3,4-b]pyridine-4-carboxylic acid ethyl esterYield 84.1%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

To a solution of 6-chloro-3-iodo-1-(tetrahydro-pyran-2-yl)-1H-pyrazolo[3,4-b]pyridine-4-carboxylic acid ethyl ester (5.00 g, 11.48 mmol) in anhydrous tetrahydrofuran (115 ml) was added tributyl(vinyl)stannane (3.52 ml, 12.05 mmol). The mixture was degassed for 15 minutes using argon, dichlorobis(triphenylphosphine)palladium (0.40 g, 0.57 mmol) was then added. The resulting solution was heated at 80° C. overnight under argon, then evaporated under reduced pressure. Ethyl acetate and a 5% aqueous potassium fluoride solution were added to the residue, the resulting precipitate was filtered. The filtrate was recovered and the two layers separated, the organic phase was washed with brine, dried (Na2SO4), filtered and concentrated under vacuum. The crude product was purified on a silica gel column chromatography using a gradient of ethyl acetate (0-10%) in cyclohexane to afford the title compound as a yellow solid (3.24 g, 84%).

Workup

  1. customThe mixture was degassed for 15 minutes
  2. additionwas then added
  3. customevaporated under reduced pressure
  4. additionEthyl acetate and a 5% aqueous potassium fluoride solution were added to the residue
  5. filtrationthe resulting precipitate was filtered
  6. customThe filtrate was recovered
  7. customthe two layers separated
  8. washthe organic phase was washed with brine
  9. dry with materialdried (Na2SO4)
  10. filtrationfiltered
  11. concentrationconcentrated under vacuum
  12. customThe crude product was purified on a silica gel column chromatography

Sources & evidence

ORD record
ord-d147ff106f8d455895e234c30fbc3080
Source dataset
uspto-grants-2014_09
Patent number
US08846712B2

Reaction notes

Loading…