Benzyl prop-2-yn-1-ylcarbamate → Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamate

HRID 49568

Reaktionsgleichung

Reaktionsgleichung von HRID 49568
Br[C:2]1[CH:3]=[CH:4][C:5]([C:8]#[C:9][CH2:10][NH:11][C:12](=[O:18])[O:13][C:14]([CH3:17])([CH3:16])[CH3:15])=[N:6][CH:7]=1.[C:19]([NH:29][CH2:30][C:31]#[CH:32])([O:21][CH2:22][C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:20]>C(NC(C)C)(C)C.C(OCC)(=O)C.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:14]([O:13][C:12]([NH:11][CH2:10][C:9]#[C:8][C:5]1[N:6]=[CH:7][C:2]([C:32]#[C:31][CH2:30][NH:29][C:19](=[O:20])[O:21][CH2:22][C:23]2[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=2)=[CH:3][CH:4]=1)=[O:18])([CH3:17])([CH3:16])[CH3:15]

Komponenten

7

Edukt 2

HCID 11137906Benzyl prop-2-yn-1-ylcarbamateHCID 21299384tert-Butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate

Produkt 1

HCID 21299383Benzyl 3-(6-{3-[(tert-butoxycarbonyl)amino]prop-1-ynyl}pyridin-3-yl)prop-2-ynylcarbamateAusbeute 55,1 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 7912DiisopropylamineLösungsmittelHCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

A mixture of tert-butyl 3-(5-bromopyridin-2-yl)prop-2-ynylcarbamate (3-1) (1.44 g), N-Cbz propargylamine (1.09 g), Pd(PPh3)2Cl2 (73 mg), and CuI (10 mg) in diisopropylamine (25 mL) was heated under reflux under a nitrogen atmosphere for 3 hours. The mixture was cooled to ambient temperature and diluted with ethyl acetate (70 mL). The precipitates were filtered and rinsed with ethyl acetate (30 mL). The filtrate and washings were combined, concentrated under reduced pressure, and purified by silica gel column chromatography using a mixture of MTBE and hexanes (2:3 to 4:1). The fractions containing the product were combined and concentrated under reduced pressure. The residue was crystallized from MTBE. Crystals were filtered, washed with MTBE, and dried to give 6-1 (1.07 g). An additional 120 mg of 6-1 was isolated from the mother liquors and washings.

Aufarbeitung

  1. temperaturewas heated
  2. temperatureunder reflux under a nitrogen atmosphere for 3 hours
  3. filtrationThe precipitates were filtered
  4. washrinsed with ethyl acetate (30 mL)
  5. concentrationconcentrated under reduced pressure
  6. custompurified by silica gel column chromatography
  7. additiona mixture of MTBE and hexanes (2:3 to 4:1)
  8. additionThe fractions containing the product
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was crystallized from MTBE
  11. filtrationCrystals were filtered
  12. washwashed with MTBE
  13. customdried

Quellen und Nachweise

ORD-Eintrag
ord-8736816034304086904f1b92f0cec74b
Quelldatensatz
uspto-grants-2004_03
Patentnummer
US06706885B2

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