Cyclopentylamine → 1-[7-(Cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone

HRID 896767

Reaktionsgleichung

Reaktionsgleichung von HRID 896767
Cl[C:2]1[N:7]2[N:8]=[C:9]([C:14]3[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=3)[C:10]([C:11](=[O:13])[CH3:12])=[C:6]2[CH:5]=[CH:4][CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH:27]1([NH2:32])[CH2:31][CH2:30][CH2:29][CH2:28]1.CCOCC>C1(C)C=CC=CC=1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.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>[CH:27]1([NH:32][C:2]2[N:7]3[N:8]=[C:9]([C:14]4[CH:19]=[CH:18][C:17]([F:20])=[CH:16][CH:15]=4)[C:10]([C:11](=[O:13])[CH3:12])=[C:6]3[CH:5]=[CH:4][CH:3]=2)[CH2:31][CH2:30][CH2:29][CH2:28]1

Komponenten

8

Edukt 4

HCID 2906CyclopentylamineHCID 3283Diethyl EtherHCID 10796Cesium carbonateHCID 223500461-(7-Chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl)ethanone

Produkt 1

HCID 121025001-[7-(Cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanoneAusbeute 96,7 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 167845palladium(II) acetateKatalysatorHCID 634876Binap, (A+-)-KatalysatorHCID 1140TolueneLösungsmittel

Versuchsvorschrift

To a solution of 1-[7-chloro-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone (2.7 g, 9.5 mmol) in toluene (50 mL) was added successively racemic-BINAP (378 mg, 0.6 mmol), cesium carbonate (4.7 g, 14.3 mmol), cyclopentylamine (4.7 mL, 47.5 mmol), and palladium(II) acetate (86 mg, 0.4 mmol). The resultant mixture was heated to 95° C. for 2.5 hours at which time the reaction was judged complete by thin layer chromatography. The solution was cooled to room temperature and ether was added. The organic layer was washed with water and brine. The aqueous layer was extracted with ether and the combined organics dried over magnesium sulfate. Filtration and concentration followed by flash chromatography (4:1 hexanes-ethyl acetate) provided 1-[7-(cyclopentylamino)-2-(4-fluorophenyl)pyrazolo[1,5-a]pyridin-3-yl]ethanone (3.1 g, 95%) as a yellow solid. 1H NMR (CDCl3): δ 7.62 (d, 1 H), 7.55 (dd, 2 H), 7.40 (t, 1 H), 7.15 (t, 2 H), 6.10 (d, 1 H), 5.99 (d, 1 H), 3.94 (m, 1 H), 2.09 (s, 3 H), 2.12-2.04 (m, 2 H), 1.78-1.58 (m, 6 H); 13C NMR (CDCl3) δ 192.63, 163.28 (d, JCF=247.3 Hz), 154.89, 142.65, 142.38, 131.66 (d, JCF=8.3 Hz) 131.09, 130.03 (d, JCF=3.8 Hz), 115.33 (d, JCF=22.0 Hz), 111.32, 105.41, 91.97, 53.81, 33.21, 30.10, 23.96; 19F NMR (CDCl3) δ −112.70; MS m/z 338 (M+1).

Aufarbeitung

  1. washThe organic layer was washed with water and brine
  2. extractionThe aqueous layer was extracted with ether
  3. dry with materialthe combined organics dried over magnesium sulfate
  4. filtrationFiltration and concentration

Quellen und Nachweise

ORD-Eintrag
ord-3f4c762d124a4767918290059c80384b
Quelldatensatz
uspto-grants-2005_07
Patentnummer
US06919352B2

Verknüpfte Notizen

Wird geladen…