Dichloromethane → Methyl trans-2-[(4'-amino-1,1'-biphenyl-4-yl)carbonyl]-cyclopropanecarboxylate

HRID 9545

反応式

HRID 9545 の反応式
Br[C:2]1[CH:16]=[CH:15][C:5]([C:6]([C@@H:8]2[CH2:10][C@H:9]2[C:11]([O:13][CH3:14])=[O:12])=[O:7])=[CH:4][CH:3]=1.[NH2:17][C:18]1[CH:23]=[CH:22][C:21](B(O)O)=[CH:20][CH:19]=1.C([O-])([O-])=O.[Na+].[Na+].ClCCl>CCOC(C)=O.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].CCO.C1(C)C=CC=CC=1>[NH2:17][C:18]1[CH:23]=[CH:22][C:21]([C:2]2[CH:16]=[CH:15][C:5]([C:6]([C@@H:8]3[CH2:10][C@H:9]3[C:11]([O:13][CH3:14])=[O:12])=[O:7])=[CH:4][CH:3]=2)=[CH:20][CH:19]=1

参加物

9

反応物 4

HCID 6344DichloromethaneHCID 10340Sodium CarbonateHCID 27346154-Aminophenylboronic acidHCID 58681311Methyl trans-2-(4-bromobenzoyl)cyclopropanecarboxylate

生成物 1

HCID 58681325Methyl trans-2-[(4'-amino-1,1'-biphenyl-4-yl)carbonyl]-cyclopropanecarboxylate収率 66.3%

試薬・触媒・溶媒 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)触媒HCID 702Ethanol溶媒HCID 1140Toluene溶媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
85 °C

実験手順

Methyl trans-2-(4-bromobenzoyl)cyclopropanecarboxylate (1.33 g, 4.70 mmol) and 4-amino-phenyl boronic acid (0.98 g, 5.64 mmol) were combined in a dry flask under argon. Toluene (25 mL), EtOH (10 mL), and 3 M aqueous Na2CO3 (7 mL, 20 mmol) were added, and the resulting solution was degassed for 30 minutes by using a flow of argon. Then [1,1′-bis(diphenylphosphino)-ferrocene]dichloro palladium(II), 1:1 complex with dichloromethane (383 mg, 0.47 mmol) was added, and the resulting mixture was heated at 85° C. for 16 h. The mixture was cooled to rt, then diluted with EtOAc and passed through a Celite® pad. The solvent was removed by rotary evaporation. Water and EtOAc were added, and the aqueous layer was extracted with EtOAc. The combined organic phases were washed with water, brine, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo. The residue was purified by flash chromatography (Biotage Flash 40M) using 33 to 40% ethyl acetate in hexane to afford methyl trans-2-[(4′-amino-1,1′-biphenyl-4-yl)carbonyl]-cyclopropanecarboxylate (0.92 g, 66%). 1H NMR (400 MHz, CD2Cl2) δ 1.60 (m, 2H), 2.35 (m, 1H), 3.22 (m, 1H), 3.73 (s, 3H), 6.80 (m, 2H), 7.51 (m, 2H), 7.68 (m, 2H), 8.05 (m, 2H).

後処理

  1. customthe resulting solution was degassed for 30 minutes
  2. temperatureThe mixture was cooled to rt
  3. customThe solvent was removed by rotary evaporation
  4. additionWater and EtOAc were added
  5. extractionthe aqueous layer was extracted with EtOAc
  6. washThe combined organic phases were washed with water, brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by flash chromatography (Biotage Flash 40M)

出典と根拠

ORDレコード
ord-b28c0f30eb30467e9c09a76d8c83cc55
出典データセット
uspto-grants-2006_08
特許番号
US07091228B2

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