Binap, (A+-)- → Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

HRID 446314

反応式

HRID 446314 の反応式
Cl[C:2]1[C:7]([C:8]2[CH:13]=[CH:12][N:11]=[CH:10][N:9]=2)=[CH:6][CH:5]=[CH:4][N:3]=1.[NH2:14][C:15]1[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=1[C:26]([F:29])([F:28])[F:27])[C:18]([O:20][CH2:21][CH3:22])=[O:19].CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C(OCC)(=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[N:11]1[CH:12]=[CH:13][C:8]([C:7]2[C:2]([NH:14][C:15]3[CH:16]=[C:17]([CH:23]=[CH:24][C:25]=3[C:26]([F:27])([F:28])[F:29])[C:18]([O:20][CH2:21][CH3:22])=[O:19])=[N:3][CH:4]=[CH:5][CH:6]=2)=[N:9][CH:10]=1

参加物

8

反応物 4

HCID 634876Binap, (A+-)-HCID 161089744-(2-Chloropyridin-3-yl)pyrimidineHCID 19783159Ethyl 3-amino-4-(trifluoromethyl)benzoateHCID 23676156Sodium t-butoxide

生成物 1

HCID 66970285Ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate

試薬・触媒・溶媒 3

HCID 167845palladium(II) acetate触媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
80 °C

実験手順

4-(2-Chloropyridin-3-yl)pyrimidine (1.5 g, 7.8 mmol), ethyl 3-amino-4-(trifluoromethyl)benzoate (2.0 g, 8.6 mmol), Sodium tert-butoxide (1.1 g, 12 mmol), rac-2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (0.49 g, 0.78 mmol) were all mixed together in toluene (25 ml) and degassed under vacuum. Nitrogen was bubbled into the reaction for 5 minutes and then Palladium (II) acetate (0.088 g, 0.39 mmol) was added. The mixture was heated to 80° C. and stirred overnight. The reaction was diluted with ethyl acetate and washed with an aqueous saturated solution of sodium bicarbonate, water and brine. The organic layer was then dried with sodium sulfate and purified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes to afford ethyl 3-(3-(pyrimidin-4-yl)pyridin-2-ylamino)-4-(trifluoromethyl)benzoate as a brown solid. MS m/z=389 [M+1]+. Calc'd for C19H15F3N4O2: 388.11.

後処理

  1. customdegassed under vacuum
  2. customNitrogen was bubbled into the reaction for 5 minutes
  3. washwashed with an aqueous saturated solution of sodium bicarbonate, water and brine
  4. dry with materialThe organic layer was then dried with sodium sulfate
  5. custompurified by column chromatography on silica gel using a gradient 5 to 40% ethyl acetate in hexanes

出典と根拠

ORDレコード
ord-f176647a0d194514a51ae28998697137
出典データセット
uspto-grants-2013_07
特許番号
US08476434B2

関連ノート

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