Tributylvinyltin → HCID 86678165, compound

HRID 82029Notes

Reaction equation

HRID 82029 reaction equation
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]([C:16]2[C:17]3[C:25](I)=[N:24][N:23]([CH:27]4[CH2:32][CH2:31][CH2:30][CH2:29][O:28]4)[C:18]=3[N:19]=[C:20]([Cl:22])[CH:21]=2)=[O:15])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[CH2:33]([Sn](CCCC)(CCCC)C=C)[CH2:34]CC>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.O1CCCC1>[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][N:11]([C:14]([C:16]2[C:17]3[C:25]([CH:33]=[CH2:34])=[N:24][N:23]([CH:27]4[CH2:32][CH2:31][CH2:30][CH2:29][O:28]4)[C:18]=3[N:19]=[C:20]([Cl:22])[CH:21]=2)=[O:15])[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 81998TributylvinyltinHCID 86678164HCID 86678164, compound

Product 1

HCID 86678165HCID 86678165, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 178418476HCID 178418476, compoundCatalystHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
80 °C

Procedure

In a 1 L single necked flask were charged 4-[6-chloro-3-iodo-1-(tetrahydro-pyran-2-yl)-1H-pyrazolo[3,4-b]pyridine-4-carbonyl]-piperazine-1-carboxylic acid tert-butyl ester (21.3 g, 37 mmol), anhydrous tetrahydrofuran (370 ml), and tributyl(vinyl)stannane (11.9 ml, 40.7 mmol). The mixture was degassed for 15 minutes using argon, dichlorobis(triphenylphosphine)palladium (1.3 g, 1.8 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 water, dried over anhydrous sodium sulfate, filtered and concentrated under vacuum. The crude product was purified on a silica gel column chromatography using a gradient of ethyl acetate (0-40%) in cyclohexane to afford the title compound as a brown foam (12.3 g, 70%).

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 water
  9. dry with materialdried over anhydrous sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under vacuum
  12. customThe crude product was purified on a silica gel column chromatography

Sources & evidence

ORD record
ord-48108efe5cb44433825ac1b972910a83
Source dataset
uspto-grants-2014_09
Patent number
US08846712B2

Reaction notes

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