Benzophenone imine → (2-Amino-pyridin-4-yl)-[3-tert-butyl-2-methoxy-5-(2-methoxy-pyridin-3-yl)-phenyl]-methanone

HRID 2390802ノート

反応式

HRID 2390802 の反応式
[C:1]([C:5]1[C:6]([O:28][CH3:29])=[C:7]([C:19]([C:21]2[CH:26]=[CH:25][N:24]=[C:23](Cl)[CH:22]=2)=[O:20])[CH:8]=[C:9]([C:11]2[C:12]([O:17][CH3:18])=[N:13][CH:14]=[CH:15][CH:16]=2)[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].C(=[NH:43])(C1C=CC=CC=1)C1C=CC=CC=1.C1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=CC=1.CC(C)([O-])C.[Na+]>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[NH2:43][C:23]1[CH:22]=[C:21]([C:19]([C:7]2[CH:8]=[C:9]([C:11]3[C:12]([O:17][CH3:18])=[N:13][CH:14]=[CH:15][CH:16]=3)[CH:10]=[C:5]([C:1]([CH3:3])([CH3:2])[CH3:4])[C:6]=2[O:28][CH3:29])=[O:20])[CH:26]=[CH:25][N:24]=1

参加物

6

反応物 4

HCID 136809Benzophenone imineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 86638337[3-Tert-butyl-2-methoxy-5-(2-methoxy-pyridin-3-yl)-phenyl]-(2-chloro-pyridin-4-yl)-methanone

生成物 1

HCID 67069931(2-Amino-pyridin-4-yl)-[3-tert-butyl-2-methoxy-5-(2-methoxy-pyridin-3-yl)-phenyl]-methanone

試薬・触媒・溶媒 1

HCID 9811564Bis(dibenzylideneacetone)palladium触媒

反応条件

温度
80 °C

実験手順

step 3—A flask containing 42 (106 mg, 0.259 mmol), benzophenone imine (0.070 mL, 0.417 mmol), Pd2(dba)3 (11.5 mg, 0.013 mmol), racemic BINAP (23.8 mg, 0.038 mmol), and sodium tert-butoxide (35 mg, 0.364 mmol) was purged with argon 3 times before toluene (5 mL) was added. The reaction was heated overnight at 80° C. then cooled to RT. The reaction mixture was diluted with EtOAc, filtered through CELITE, and the filtrate was concentrated. The residue was taken up in a mixture of MeOH (5 mL) and hydroxylamine (50% wt solution in water, 0.5 mL) and stirred overnight at RT before it was concentrated. The crude residue was purified by SiO2 chromatography eluting with an EtOAc/hexane gradient (25 to 75% EtOAc) to afford (2-amino-pyridin-4-yl)-[3-tert-butyl-2-methoxy-5-(2-methoxy-pyridin-3-yl)-phenyl]-methanone (44) as a pale yellow oil.

後処理

  1. customwas purged with argon 3 times before toluene (5 mL)
  2. additionwas added
  3. temperaturethen cooled to RT
  4. additionThe reaction mixture was diluted with EtOAc
  5. filtrationfiltered through CELITE
  6. concentrationthe filtrate was concentrated
  7. additionThe residue was taken up in a mixture of MeOH (5 mL) and hydroxylamine (50% wt solution in water, 0.5 mL)
  8. concentrationwas concentrated
  9. customThe crude residue was purified by SiO2 chromatography
  10. washeluting with an EtOAc/hexane gradient (25 to 75% EtOAc)

出典と根拠

ORDレコード
ord-b4c9845cf3a0435faea072184ea876ce
出典データセット
uspto-grants-2012_09
特許番号
US08273773B2

反応ノート

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