Binap, (A+-)- → tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoate

HRID 42003ノート

反応式

HRID 42003 の反応式
[NH2:1][C:2]1[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=1[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5].[Br:16][C:17]1[CH:22]=[CH:21][C:20](I)=[CH:19][N:18]=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([O-])(C)C.[Na+]>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].C(OCC)(=O)C.O>[Br:16][C:17]1[N:18]=[CH:19][C:20]([NH:1][C:2]2[CH:14]=[CH:13][C:12]([CH3:15])=[CH:11][C:3]=2[C:4]([O:6][C:7]([CH3:10])([CH3:9])[CH3:8])=[O:5])=[CH:21][CH:22]=1

参加物

9

反応物 4

HCID 634876Binap, (A+-)-HCID 47382712-Bromo-5-iodopyridineHCID 13399998tert-Butyl 2-amino-5-methylbenzoateHCID 23676156Sodium t-butoxide

生成物 1

HCID 86657255tert-Butyl 2-(6-bromopyridin-3-ylamino)-5-methylbenzoate収率 40.2%

試薬・触媒・溶媒 4

HCID 9811564Bis(dibenzylideneacetone)palladium触媒HCID 962Water溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
120 °C

実験手順

In a schlenck tube, a mixture of tert-butyl 2-amino-5-methylbenzoate (2.89 mmol, 0.600 g), 2-bromo-5-iodopyridine (2.89 mmol, 0.822 g), BINAP (0.29 mmol, 0.096 g), Pd2(dba)3 (0.14 mmol, 0.132 g) and NaOtBu (5.79 mmol, 0.556 g) in toluene (15 ml) was heated at 120° C. for 3 hours. Water and ethyl acetate were added to the reaction crude. The aqueous phase was extracted again with more ethyl acetate. The organic phase was washed with water and brine, dried, filtered and concentrated in vacuo. The crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%) affording 0.422 g (yield 40%) of the expected product.

後処理

  1. extractionThe aqueous phase was extracted again with more ethyl acetate
  2. washThe organic phase was washed with water and brine
  3. customdried
  4. filtrationfiltered
  5. concentrationconcentrated in vacuo
  6. customThe crude mixture was purified by chromatography (Biotage 40S, SiO2, Hexane:Ethyl acetate from 0% to 10%)

出典と根拠

ORDレコード
ord-526c59565f6c4553ab53563a4218665a
出典データセット
uspto-grants-2013_09
特許番号
US08536165B2

反応ノート

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