Sodium Carbonate → 5-(6,7-Dihydropyrido[3,2-b]thieno[2,3-d]oxepin-9-yl)pyridin-2-nitrile

HRID 1949867Notes

Reaction equation

HRID 1949867 reaction equation
Br[C:2]1[S:15][C:5]2[C:6]3[N:14]=[CH:13][CH:12]=[CH:11][C:7]=3[O:8][CH2:9][CH2:10][C:4]=2[CH:3]=1.B1([C:25]2[CH:30]=[CH:29][C:28]([C:31]#[N:32])=[N:27][CH:26]=2)OC(C)(C)C(C)(C)O1.C(=O)([O-])[O-].[Na+].[Na+]>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl.C(#N)C>[N:14]1[C:6]2[C:5]3[S:15][C:2]([C:25]4[CH:30]=[CH:29][C:28]([C:31]#[N:32])=[N:27][CH:26]=4)=[CH:3][C:4]=3[CH2:10][CH2:9][O:8][C:7]=2[CH:11]=[CH:12][CH:13]=1

Participants

6

Reactant 3

HCID 10340Sodium CarbonateHCID 164141882-Cyanopyridine-5-boronic acid pinacol esterHCID 579004919-Bromo-6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepine

Product 1

HCID 668690225-(6,7-Dihydropyrido[3,2-b]thieno[2,3-d]oxepin-9-yl)pyridin-2-nitrile

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 6342AcetonitrileSolvent

Procedure

A mixture of 80 mg (0.3 mmol) of 9-bromo-6,7-dihydro-pyrido[3,2-b]thieno[2,3-d]oxepine, 78.3 (0.34 mmol), 2-cyanopyridine-5-boronic acid pinacole ester, and 10 mg (0.014 mmol) of bis(triphenylphosphine)palladium (II) chloride in 0.35 ml (0.35 mmol) of aqueous 1 M solution of sodium carbonate and 4 ml of acetonitrile was degassed and microwaved on 200 Wt at 140° C. for 30 min. the reaction mixture was filtered through celite and partitioned between ethyl acetate and water. The organic layer was washed with water, brine dried over sodium sulfate and concentrated in vacuum. The residue was purified on a 4 g silica column eluting with 10% of methanol in dichloromethane to give 5-(6,7-dihydropyrido[3,2-b]thieno[2,3-d]oxepin-9-yl)pyridin-2-nitrile. Yield 27 mg (30%). MS: (ESI+) 306.1

Workup

  1. customwas degassed
  2. custommicrowaved on 200 Wt at 140° C. for 30 min. the reaction mixture
  3. filtrationwas filtered through celite
  4. custompartitioned between ethyl acetate and water
  5. washThe organic layer was washed with water, brine
  6. dry with materialdried over sodium sulfate
  7. concentrationconcentrated in vacuum
  8. customThe residue was purified on a 4 g silica column
  9. washeluting with 10% of methanol in dichloromethane

Sources & evidence

ORD record
ord-9b0decccd55d401dae322e1cb7f2b9d6
Source dataset
uspto-grants-2013_03
Patent number
US08399690B2

Reaction notes

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