Cesium carbonate → tert-butyl 3-(6-((diphenylmethylene)amino)-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate

HRID 919646Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 919646
Br[C:2]1[N:7]=[CH:6][C:5]2[N:8]=[CH:9][N:10]([CH:11]3[CH2:16][CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12]3)[C:4]=2[CH:3]=1.[NH:24](C1C=CC=CC=1)C1C=CC=CC=1.C[C:38]1(C)[C:64]2[C:59](=[C:60](P(C3C=CC=CC=3)C3C=CC=CC=3)[CH:61]=[CH:62][CH:63]=2)O[C:40]2[C:41](P(C3C=CC=CC=3)C3C=CC=CC=3)=[CH:42][CH:43]=[CH:44][C:39]1=2.C([O-])([O-])=O.[Cs+].[Cs+]>CC(N(C)C)=O>[C:39]1([C:38](=[N:24][C:2]2[N:7]=[CH:6][C:5]3[N:8]=[CH:9][N:10]([CH:11]4[CH2:16][CH2:15][CH2:14][N:13]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:12]4)[C:4]=3[CH:3]=2)[C:64]2[CH:59]=[CH:60][CH:61]=[CH:62][CH:63]=2)[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1

Komponenten

6

Edukt 4

HCID 10796Cesium carbonateHCID 11487DiphenylamineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 72344680tert-butyl 3-(6-bromo-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate

Produkt 1

HCID 87946249tert-butyl 3-(6-((diphenylmethylene)amino)-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylateAusbeute 519,1 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 31374DimethylacetamideLösungsmittel

Reaktionsbedingungen

Temperatur
115 °C

Versuchsvorschrift

To a solution of tert-butyl 3-(6-bromo-1H-imidazo[4,5-c]pyridin-1-yl)piperidine-1-carboxylate (0.6 g, 1.58 mmol, 1.0 eq) in DMA (5 mL) were added Ph2NH (430 mg, 2.37 mmol, 1.5 eq), Pd3(dba)2 (87 mg, 0.095 mmol, 0.06 eq), Xantphos (91 mg, 0.16 mmol, 0.1 eq) and Cs2CO3 (0.8 g, 2.5 mmol, 1.6 eq) at rt under N2. The mixture was stirred at 115° C. for 16 h, cooled to rt and the solid was filtered off and washed with EtOAc (30 mL). The organic layer was washed with H2O (20 mL×2) and brine (10 mL), separated, dried (Na2SO4) and concentration in vacuo to afford a residue which was purified by silica gel column chromatography with EtOAc in PE (1/1 v/v) to give the title compound (0.4 g, 50%) as brown solid. 1H NMR (400 MHz, CDCl3) δ: 8.80 (s, 1H), 7.89 (s, 1H), 7.82 (d, 2H), 7.52-7.48 (m, 1H), 7.44-7.40 (m, 2H), 7.27-7.24 (m, 3H), 7.24-7.17 (m, 2H), 6.68 (s, 1H), 4.13-4.09 (m, 2H), 3.95-3.92 (m, 1H), 3.18-3.14 (m, 1H), 3.01-2.94 (m, 1H), 1.95-1.90 (m, 2H), 1.79-1.76 (m, 1H), 1.63-1.60 (m, 1H), 1.53 (s, 9H). ESI-MS (M+H+): 382.0.

Aufarbeitung

  1. temperaturecooled to rt
  2. filtrationthe solid was filtered off
  3. washwashed with EtOAc (30 mL)
  4. washThe organic layer was washed with H2O (20 mL×2) and brine (10 mL)
  5. customseparated
  6. customdried
  7. concentration(Na2SO4) and concentration in vacuo
  8. customto afford a residue which
  9. customwas purified by silica gel column chromatography with EtOAc in PE (1/1 v/v)

Quellen und Nachweise

ORD-Eintrag
ord-16ce8639513c4a3298d40d611f1635a4
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09273028B2

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