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

HRID 9545

Reaktionsgleichung

Reaktionsgleichung von HRID 9545
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

Komponenten

9

Edukt 4

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

Produkt 1

HCID 58681325Methyl trans-2-[(4'-amino-1,1'-biphenyl-4-yl)carbonyl]-cyclopropanecarboxylateAusbeute 66,3 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 702EthanolLösungsmittelHCID 1140TolueneLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Reaktionsbedingungen

Temperatur
85 °C

Versuchsvorschrift

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).

Aufarbeitung

  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)

Quellen und Nachweise

ORD-Eintrag
ord-b28c0f30eb30467e9c09a76d8c83cc55
Quelldatensatz
uspto-grants-2006_08
Patentnummer
US07091228B2

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