Potassium Carbonate → 6'-(1H-indazol-4-yl)dispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-amine

HRID 873755ノート

反応式

HRID 873755 の反応式
Br[C:2]1[CH:3]=[C:4]2[C:31](=[CH:32][CH:33]=1)[O:30][CH2:29][C:25]1([CH2:28][O:27][CH2:26]1)[C:5]12[CH2:9][O:8][C:7]([N:10](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)=[N:6]1.O1CCOCC1.[NH:40]1[C:48]2[C:43](=[C:44](B(O)O)[CH:45]=[CH:46][CH:47]=2)[CH:42]=[N:41]1.C([O-])([O-])=O.[K+].[K+]>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.O>[NH:40]1[C:48]2[C:43](=[C:44]([C:2]3[CH:3]=[C:4]4[C:31](=[CH:32][CH:33]=3)[O:30][CH2:29][C:25]3([CH2:28][O:27][CH2:26]3)[C:5]34[CH2:9][O:8][C:7]([NH2:10])=[N:6]3)[CH:45]=[CH:46][CH:47]=2)[CH:42]=[N:41]1

参加物

7

反応物 4

HCID 11430Potassium CarbonateHCID 312751,4-DioxaneHCID 441183101H-Indazole-4-boronic acidHCID 86724239Di-tert-butyl (6'-bromodispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-yl)imidodicarbonate

生成物 1

HCID 867243066'-(1H-indazol-4-yl)dispiro[1,3-oxazole-4,4'-chromene-3',3''-oxetan]-2-amine収率 68.6%

試薬・触媒・溶媒 2

HCID 178418476HCID 178418476、化合物触媒HCID 962Water溶媒

反応条件

温度
100 °C

実験手順

Under argon atmosphere, to a mixture of di-tert-butyl (6′-bromodispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-yl)imidodicarbonate (300 mg, 0.571 mmol), dioxane (3.0 mL) and water (1.5 mL) were added 1H-indazol-4-ylboronic acid (185 mg, 1.14 mmol), K2CO3 (237 mg, 1.71 mmol) and bis(triphenylphosphine)palladium(II) dichloride (40 mg, 0.057 mmol), and the mixture was stirred for 3 hours at 100° C. The reaction mixture was cooled down to ambient temperature, partitioned between H2O and 10% MeOH in CHCl3. The organic layer was dried over Na2SO4 and filtered, and the filtrate was concentrated at reduced pressure. The residue was dissolved with dioxane (3.0 mL), and silica gel (neutral; 900 mg) was added to the mixture. After stirring for 2.5 hours at 110° C., the reaction mixture was cooled down to ambient temperature, and concentrated at reduced pressure. Purification of the residue with column chromatography on silica gel (CHCl3-EtOH, a linear gradient of EtOH from 0 to 20%) afforded 6′-(1H-indazol-4-yl)dispiro[1,3-oxazole-4,4′-chromene-3′,3″-oxetan]-2-amine (142 mg).

後処理

  1. temperatureThe reaction mixture was cooled down to ambient temperature
  2. custompartitioned between H2O and 10% MeOH in CHCl3
  3. dry with materialThe organic layer was dried over Na2SO4
  4. filtrationfiltered
  5. concentrationthe filtrate was concentrated at reduced pressure
  6. dissolutionThe residue was dissolved with dioxane (3.0 mL), and silica gel (neutral; 900 mg)
  7. additionwas added to the mixture
  8. stirringAfter stirring for 2.5 hours at 110° C.
  9. temperaturethe reaction mixture was cooled down to ambient temperature
  10. concentrationconcentrated at reduced pressure
  11. customPurification of the residue with column chromatography on silica gel (CHCl3-EtOH

出典と根拠

ORDレコード
ord-c6773bcc93c6420eb7c36b2b1aba2886
出典データセット
uspto-grants-2015_03
特許番号
US08975415B2

反応ノート

読み込み中…