Water → methyl 2-(tert-butoxy)-2-[3-(3,4-dihydro-2H-1-benzopyran-6-yl)thieno[2,3-b]pyridin-2-yl]acetate

HRID 591009Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 591009
C(=O)([O-])[O-].[Na+].[Na+].O.CC1(C)C(C)(C)OB([C:16]2[CH:17]=[C:18]3[C:23](=[CH:24][CH:25]=2)[O:22][CH2:21][CH2:20][CH2:19]3)O1.Br[C:28]1[C:36]2[C:31](=[N:32][CH:33]=[CH:34][CH:35]=2)[S:30][C:29]=1[CH:37]([O:42][C:43]([CH3:46])([CH3:45])[CH3:44])[C:38]([O:40][CH3:41])=[O:39]>CN(C)C=O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd]>[C:43]([O:42][CH:37]([C:29]1[S:30][C:31]2=[N:32][CH:33]=[CH:34][CH:35]=[C:36]2[C:28]=1[C:16]1[CH:25]=[CH:24][C:23]2[O:22][CH2:21][CH2:20][CH2:19][C:18]=2[CH:17]=1)[C:38]([O:40][CH3:41])=[O:39])([CH3:46])([CH3:44])[CH3:45]

Komponenten

7

Edukt 4

HCID 962WaterHCID 10340Sodium CarbonateHCID 438110342-(3,4-dihydro-2H-1-benzopyran-6-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolaneHCID 70855404Methyl 2-{3-bromothieno[2,3-b]pyridin-2-yl}-2-(tert-butoxy)acetate

Produkt 1

HCID 70855407methyl 2-(tert-butoxy)-2-[3-(3,4-dihydro-2H-1-benzopyran-6-yl)thieno[2,3-b]pyridin-2-yl]acetateAusbeute 49 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
110 °C

Versuchsvorschrift

Under a nitrogen atmosphere, sodium carbonate (16 mg, 0.15 mmol), water (1 mL), palladium tetrakis(triphenylphosphine) (27 mg, 0.02 mmol) and 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)chroman (40 mg, 0.15 mmol) were added to a solution of methyl 2-{3-bromothieno[2,3-b]pyridin-2-yl}-2-(tert-butoxy)acetate (14g) (55 mg, 0.15 mmol) in N,N-dimethylformamide (4 mL). The mixture was heated at 110° C. for 1 hour. The mixture was then cooled at room temperature, concentrated and water (20 mL) was added. The aqueous layer was extracted with ethyl acetate (2×20 mL). The organic layer was washed with brine (20 mL), dried over sodium sulfate, filtered and evaporated under reduced pressure. The residue was purified by flash chromatography on silica gel (dichloromethane/ethyl acetate 90/10) to afford the desired product (14h) as a white solid (30 mg, 0.07 mmol, 49%).

Aufarbeitung

  1. temperatureThe mixture was then cooled at room temperature
  2. concentrationconcentrated
  3. additionwater (20 mL) was added
  4. extractionThe aqueous layer was extracted with ethyl acetate (2×20 mL)
  5. washThe organic layer was washed with brine (20 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customevaporated under reduced pressure
  9. customThe residue was purified by flash chromatography on silica gel (dichloromethane/ethyl acetate 90/10)

Quellen und Nachweise

ORD-Eintrag
ord-a3c273093bd7468c81dff10f0aee832e
Quelldatensatz
uspto-grants-2016_01
Patentnummer
US09238026B2

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