Binap, (A+-)- → ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylate

HRID 516255Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 516255
[NH2:1][C@H:2]([CH3:22])[CH2:3][O:4][C:5]1[C:20](Br)=[CH:19][C:8]2[CH2:9][CH2:10][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:12][CH2:13][C:7]=2[CH:6]=1.CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1(C)C=CC=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:22][C@@H:2]1[CH2:3][O:4][C:5]2[C:20](=[CH:19][C:8]3[CH2:9][CH2:10][N:11]([C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH2:12][CH2:13][C:7]=3[CH:6]=2)[NH:1]1

Komponenten

6

Edukt 3

HCID 634876Binap, (A+-)-2×HCID 23676156Sodium t-butoxide2×HCID 58495302HCID 58495302, Verbindung

Produkt 1

HCID 66982702ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylateAusbeute 47,6 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 9811564Bis(dibenzylideneacetone)palladiumKatalysator2×HCID 1140TolueneLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

Under an argon atmosphere, to a solution of 1.64 g of ethyl 7-{[(2R)-2-aminopropyl]oxy}-8-bromo-1,2,4,5-tetrahydro-3H-3-benzazepine-3-carboxylate in 41 ml of toluene were added 509 mg of sodium t-butoxide, 275 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 202 mg of tris(dibenzylideneacetone)dipalladium (0) in this order, followed by heating at 100° C. for 24 hours. Further, 509 mg of sodium t-butoxide, 275 mg of 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl, and 202 mg of tris(dibenzylideneacetone)dipalladium (0) were added thereto, followed by stirring at 100° C. for additional 24 hours. The reaction mixture was returned to room temperature, then filtered through celite, and washed with ethyl acetate, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel chromatography (elution solvent: Hex-AcOEt) to obtain 610 mg of ethyl (3R)-3-methyl-3,4,6,7,9,10-hexahydro[1,4]oxazino[2,3-h][3]benzazepine-8(2H)-carboxylate.

Aufarbeitung

  1. customwas returned to room temperature
  2. filtrationfiltered through celite
  3. washwashed with ethyl acetate
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. customThe residue was purified by silica gel chromatography (elution solvent: Hex-AcOEt)

Quellen und Nachweise

ORD-Eintrag
ord-f5566578c8604758814880f0bff960dc
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09108977B2

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