Methyl Acrylate → (E)-3-{1'-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4'-piperidine]-6-yl}-acrylic acid methyl ester

HRID 518147

Reaktionsgleichung

Reaktionsgleichung von HRID 518147
[C:1]([O:5][C:6]([N:8]1[CH2:13][CH2:12][C:11]2([CH2:22][C:21](=[O:23])[C:20]3[C:15](=[CH:16][CH:17]=[C:18](Br)[CH:19]=3)[O:14]2)[CH2:10][CH2:9]1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[C:44]([O:48][CH3:49])(=[O:47])[CH:45]=[CH2:46]>CN(C=O)C.CC([O-])=O.CC([O-])=O.[Pd+2]>[CH3:49][O:48][C:44](=[O:47])/[CH:45]=[CH:46]/[C:18]1[CH:19]=[C:20]2[C:15](=[CH:16][CH:17]=1)[O:14][C:11]1([CH2:12][CH2:13][N:8]([C:6]([O:5][C:1]([CH3:4])([CH3:3])[CH3:2])=[O:7])[CH2:9][CH2:10]1)[CH2:22][C:21]2=[O:23]

Komponenten

6

Edukt 3

HCID 7294Methyl AcrylateHCID 11776TriphenylphosphineHCID 2794759tert-Butyl 6-bromo-4-oxospiro[chroman-2,4'-piperidine]-1'-carboxylate

Produkt 1

HCID 52952087(E)-3-{1'-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4'-piperidine]-6-yl}-acrylic acid methyl esterAusbeute 56,5 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 167845palladium(II) acetateKatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
100 °C

Versuchsvorschrift

A mixture of 6-bromo-4-oxo-spiro[chromane-2,4′-piperidine]-1′-carboxylic acid tert-butyl ester (1.04 g, 2.62 mmol), Pd(OAc)2 (59 mg, 0.262 mmol), PPh3 (137 mg, 0.52 mmol), TEA (0.73 ml, 5.2 mmol), methyl acrylate (0.47 ml, 5.2 mmol) in dry DMF (10 ml) was heated at 100° C. for 8 h. The mixture was cooled down to RT, filtered on a celite pad and washed with AcOEt (100 ml). The filtrate was washed with NH4Cl and saturated NaHCO3 solution and brine. The organic phase was dried over Na2SO4 and evaporated under vacuum. The crude residue was purified by column chromatography (eluent: hexane/AcOEt 90:10 to 70:30) to give (E)-3-{1′-tert-butoxycarbonyl-4-oxo-spiro[chromane-2,4′-piperidine]-6-yl}-acrylic acid methyl ester (594 mg) as a light yellow solid.

Aufarbeitung

  1. temperatureThe mixture was cooled down to RT
  2. filtrationfiltered on a celite pad
  3. washwashed with AcOEt (100 ml)
  4. washThe filtrate was washed with NH4Cl and saturated NaHCO3 solution and brine
  5. dry with materialThe organic phase was dried over Na2SO4
  6. customevaporated under vacuum
  7. customThe crude residue was purified by column chromatography (eluent: hexane/AcOEt 90:10 to 70:30)

Quellen und Nachweise

ORD-Eintrag
ord-f9ad2718e899439abea27c2aeec88001
Quelldatensatz
uspto-grants-2015_08
Patentnummer
US09115148B2

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