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

HRID 591009ノート

反応式

HRID 591009 の反応式
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]

参加物

7

反応物 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

生成物 1

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

試薬・触媒・溶媒 2

HCID 11979704Tetrakis(triphenylphosphine)palladium触媒HCID 6228Dimethylformamide溶媒

反応条件

温度
110 °C

実験手順

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%).

後処理

  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)

出典と根拠

ORDレコード
ord-a3c273093bd7468c81dff10f0aee832e
出典データセット
uspto-grants-2016_01
特許番号
US09238026B2

反応ノート

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