2-(Di-tert-butylphosphino)biphenyl → 6'-Isobutyltrispiro[cyclobutane-1,2'-chromene-4',4''-[1,3]oxazole-3',3'''-oxetan]-2''-amine

HRID 594898ノート

反応式

HRID 594898 の反応式
[C:1]1([C:16]2C=CC=CC=2)[CH:6]=CC=C[C:2]=1P(C(C)(C)C)C(C)(C)C.Br[C:23]1[CH:24]=[C:25]2[C:38]3([CH2:42][O:41][C:40]([N:43](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)=[N:39]3)[C:34]3([CH2:37][O:36][CH2:35]3)[C:30]3([CH2:33][CH2:32][CH2:31]3)[O:29][C:26]2=[CH:27][CH:28]=1.[Br-].C([Zn+])C(C)C>C1COCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:2]([C:23]1[CH:24]=[C:25]2[C:38]3([CH2:42][O:41][C:40]([NH2:43])=[N:39]3)[C:34]3([CH2:37][O:36][CH2:35]3)[C:30]3([CH2:31][CH2:32][CH2:33]3)[O:29][C:26]2=[CH:27][CH:28]=1)[CH:1]([CH3:16])[CH3:6]

参加物

6

反応物 3

HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 86724300Di-tert-butyl (6'-bromotrispiro[cyclobutane-1,2'-chromene-4',4''-[1,3]oxazole-3',3'''-oxetan]-2''-yl)imidodicarbonateHCID 178448254HCID 178448254、化合物

生成物 1

HCID 867242996'-Isobutyltrispiro[cyclobutane-1,2'-chromene-4',4''-[1,3]oxazole-3',3'''-oxetan]-2''-amine収率 324.5%

試薬・触媒・溶媒 2

HCID 167845palladium(II) acetate触媒HCID 8028Tetrahydrofuran溶媒

実験手順

To a stirred mixture of palladium (II) acetate (7.9 mg, 0.035 mmol) and biphenyl-2-yl(di-tert-butyl)phosphine (5.3 mg, 0.018 mmol) in THF (5 mL) under argon atmosphere was added di-tert-butyl (6′-bromotrispiro[cyclobutane-1,2′-chromene-4′,4″-[1,3]oxazole-3′,3′″-oxetan]-2″-yl)imidodicarbonate (100 mg, 0.177 mmol) followed by isobutylzinc bromide (0.5 M THF solution, 1.1 mL). The reaction mixture was stirred at room temperature for 17 hours, and then the reaction was quenched with H2O and brine. The resulting mixture was extracted with chloroform 3 times. The combined organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The crude product was dissolved in toluene (6 mL). To the solution was added silica gel (neutral; 600 mg), and the resulting suspension was stirred at 100° C. for 1 hour. After cooling and concentration, the residue was purified by silica gel column chromatography (EtOH/CHCl3=0:100-20:80) followed by column chromatography (NH-silica gel, EtOAc/hexane=20:80-100:0) to afford 6′-isobutyltrispiro[cyclobutane-1,2′-chromene-4′,4″-[1,3]oxazole-3′,3′″-oxetan]-2″-amine (20 mg).

後処理

  1. customthe reaction was quenched with H2O and brine
  2. extractionThe resulting mixture was extracted with chloroform 3 times
  3. dry with materialThe combined organic layer was dried over magnesium sulfate
  4. concentrationconcentrated under reduced pressure
  5. dissolutionThe crude product was dissolved in toluene (6 mL)
  6. additionTo the solution was added silica gel (neutral; 600 mg)
  7. stirringthe resulting suspension was stirred at 100° C. for 1 hour
  8. temperatureAfter cooling
  9. concentrationconcentration
  10. customthe residue was purified by silica gel column chromatography (EtOH/CHCl3=0:100-20:80)

出典と根拠

ORDレコード
ord-781b5d3e672b4d459a877c48851accbc
出典データセット
uspto-grants-2016_01
特許番号
US09242973B2

反応ノート

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