1,2,3,6-Tetrahydropyridine → tert-Butyl 4-(5,6-dihydropyridin-1(2H)-yl)piperidine-1-carboxylate

HRID 501957

Reaktionsgleichung

Reaktionsgleichung von HRID 501957
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11](=O)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].[NH:15]1[CH2:20][CH:19]=[CH:18][CH2:17][CH2:16]1.C([BH3-])#N.[Na+]>[Cl-].[Zn+2].[Cl-].CO>[N:15]1([CH:11]2[CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]2)[CH2:20][CH2:19][CH:18]=[CH:17][CH2:16]1

Komponenten

6

Edukt 3

HCID 127501,2,3,6-TetrahydropyridineHCID 735900tert-Butyl 4-oxopiperidine-1-carboxylateHCID 5003444Sodium cyanoborohydride

Produkt 1

HCID 59424368tert-Butyl 4-(5,6-dihydropyridin-1(2H)-yl)piperidine-1-carboxylate

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3007855ZincchlorideKatalysatorHCID 887MethanolLösungsmittel

Versuchsvorschrift

4-Oxo-piperidine-1-carboxylic acid tert-butyl ester (797 mg, 4 mmol), 1,2,3,6-tetrahydropyridine (349 mg, 4.2 mmol), sodium cyanoborohydride (126 mg, 2 mmol), zinc chloride (410 mg, 3.2 mmol), and anhydrous methanol (20 mL) were mixed together and the mixture stirred overnight at room temperature. The solvent was evaporated from the mixture and the residue partitioned between 1 N sodium hydroxide and dichloromethane. The phases were separated and the aqueous layer extracted with dichloromethane. The organic extracts were combined, dried over magnesium sulfate, and the solvent evaporated. The residue was purified by flash column chromatography (1:1 hexanes/ethyl acetate to ethyl acetate to 1:3 methanol/ethyl acetate) to give 800 mg (75%) as a colorless oil. 1H-NMR (CDCl3, 400 MHz) δ 5.75-5.70 (m, 1H), 5.68-5.64 (m, 1H), 4.13-4.07 (m, 2H), 3.08 (m, 2H), 2.71-2.60 (m, 4H), 2.48-2.41 (m, 1H), 2.15 (m, 2H), 1.82-1.79 (m, 2H), 1.49-1.38 (m, 11H).

Aufarbeitung

  1. customThe solvent was evaporated from the mixture
  2. customthe residue partitioned between 1 N sodium hydroxide and dichloromethane
  3. customThe phases were separated
  4. extractionthe aqueous layer extracted with dichloromethane
  5. dry with materialdried over magnesium sulfate
  6. customthe solvent evaporated
  7. customThe residue was purified by flash column chromatography (1:1 hexanes/ethyl acetate to ethyl acetate to 1:3 methanol/ethyl acetate)
  8. customto give 800 mg (75%) as a colorless oil

Quellen und Nachweise

ORD-Eintrag
ord-38ba99de91ff427386a7fe8cf8cd7404
Quelldatensatz
uspto-grants-2010_08
Patentnummer
US07772244B2

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