tert-butyl 4-((5-bromo-1-isopropyl-1H-pyrazol-4-yl)methyl)-4-isocyanatopiperidine-1-carboxylate → Tert-butyl 1'-isopropyl-7'-oxo-1',4',6',7'-tetrahydrospiro[piperidine-4,5'-pyrazolo[3,4-c]pyridine]-1-carboxylate

HRID 537099Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 537099
Br[C:2]1[N:6]([CH:7]([CH3:9])[CH3:8])[N:5]=[CH:4][C:3]=1[CH2:10][C:11]1([N:24]=[C:25]=[O:26])[CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])[CH2:13][CH2:12]1.C([Li])(C)(C)C>CC1CCCO1>[CH:7]([N:6]1[C:2]2[C:25](=[O:26])[NH:24][C:11]3([CH2:16][CH2:15][N:14]([C:17]([O:19][C:20]([CH3:21])([CH3:23])[CH3:22])=[O:18])[CH2:13][CH2:12]3)[CH2:10][C:3]=2[CH:4]=[N:5]1)([CH3:8])[CH3:9]

Komponenten

4

Edukt 2

HCID 71507904tert-butyl 4-((5-bromo-1-isopropyl-1H-pyrazol-4-yl)methyl)-4-isocyanatopiperidine-1-carboxylateHCID 178418306HCID 178418306, Verbindung

Produkt 1

HCID 67491663Tert-butyl 1'-isopropyl-7'-oxo-1',4',6',7'-tetrahydrospiro[piperidine-4,5'-pyrazolo[3,4-c]pyridine]-1-carboxylateAusbeute 67 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 73012-MethyltetrahydrofuranLösungsmittel

Versuchsvorschrift

To a mixture of tert-butyl 4-((5-bromo-1-isopropyl-1H-pyrazol-4-yl)methyl)-4-isocyanatopiperidine-1-carboxylate (1.4 g, 3.3 mmol) in 2-methyl tetrahydrofuran (10 mL) was added t-butyl lithium (1.7 M in hexane, 4.3 mL, 7.2 mmol) at −78° C., under argon. After the addition was complete the mixture was allowed to warm to room temperature and was stirred for 18 hours. The mixture was quenched with water (10 mL) and then diluted with ethyl acetate (20 mL). The layers were separated and the organic layer was washed with brine (10 mL), dried over sodium sulfate, filtered and the solvent removed in vacuo. The crude product was purified by flash column chromatography to give tert-butyl 1′-isopropyl-7′-oxo-1′,4′,6′,7′-tetrahydrospiro[piperidine-4,5′-pyrazolo[3,4-c]pyridine]-1-carboxylate (0.77 g, 67%). +ESI (M+H) 374.1; 1H NMR (300 MHz, CDCl3, δ): 7.34 (s, 1H), 6.35 (s, 1H), 5.45 (m, 1H), 3.57 (m, 2H), 3.42 (m, 2H), 2.79 (s, 2H), 1.70 (m, 4H), 1.45 (m, 15H).

Aufarbeitung

  1. additionAfter the addition
  2. customThe mixture was quenched with water (10 mL)
  3. additiondiluted with ethyl acetate (20 mL)
  4. customThe layers were separated
  5. washthe organic layer was washed with brine (10 mL)
  6. dry with materialdried over sodium sulfate
  7. filtrationfiltered
  8. customthe solvent removed in vacuo
  9. customThe crude product was purified by flash column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-d210d15021d54caa93582d3771cd64e7
Quelldatensatz
uspto-grants-2014_10
Patentnummer
US08859773B2

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