Cesium carbonate → Benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)cyclopropyl)-3-fluorophenyl)acrylate

HRID 1842902Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1842902
[C:1]([Si:5]([O:8][C:9]1([C:12]2[CH:17]=[CH:16][C:15](B3OC(C)(C)C(C)(C)O3)=[CH:14][C:13]=2[F:27])[CH2:11][CH2:10]1)([CH3:7])[CH3:6])([CH3:4])([CH3:3])[CH3:2].C([O-])([O-])=O.[Cs+].[Cs+].Br[C:35](=[CH2:46])[C:36]([O:38][CH2:39][C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=1)=[O:37]>CN(C=O)C.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2]>[Si:5]([O:8][C:9]1([C:12]2[CH:17]=[CH:16][C:15]([C:35](=[CH2:46])[C:36]([O:38][CH2:39][C:40]3[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=3)=[O:37])=[CH:14][C:13]=2[F:27])[CH2:11][CH2:10]1)([C:1]([CH3:2])([CH3:4])[CH3:3])([CH3:7])[CH3:6]

Komponenten

6

Edukt 3

HCID 10796Cesium carbonateHCID 13443472Benzyl 2-bromoprop-2-enoateHCID 70815542Tert-butyl(1-(2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropoxy)-dimethylsilane

Produkt 1

HCID 86672144Benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)cyclopropyl)-3-fluorophenyl)acrylateAusbeute 37,2 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)KatalysatorHCID 6228DimethylformamideLösungsmittel

Reaktionsbedingungen

Temperatur
95 °C

Versuchsvorschrift

To a stirred and degassed (degassed with Argon) suspension of tert-butyl(1-(2-fluoro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclopropoxy)-dimethylsilane (10.23 g, 26.09 mmol, leg), Cs2CO3 (30.69 g, 78.27 mmol, 3 eq), and benzyl 2-bromoacrylate (9.59 g, 39.14 mmol, 1.5 eq) in DMF (100 mL) was added Pd(dppf)Cl2 (1.06 g, 1.305 mmol, 0.05 eq) and the mixture heated to 90-100° C. for 1 h. The reaction mixture was filtered through celite pad, diluted with water (100 mL) and extracted with ethyl acetate (250 mL). The ethyl acetate layer was washed with water (150 mL), brine (200 mL), dried (Na2SO4) and the solvent evaporated to get crude benzyl 2-(4-(1-(tert-butyldimethylsilyloxy)-cyclopropyl)-3-fluorophenyl)acrylate (4.14 g) as a yellow oil which was used for the next stage without purification (TLC system: EtOAc/PE (1:49), Rf: 0.5).

Aufarbeitung

  1. customdegassed
  2. filtrationThe reaction mixture was filtered through celite pad
  3. additiondiluted with water (100 mL)
  4. extractionextracted with ethyl acetate (250 mL)
  5. washThe ethyl acetate layer was washed with water (150 mL), brine (200 mL)
  6. dry with materialdried (Na2SO4)
  7. customthe solvent evaporated

Quellen und Nachweise

ORD-Eintrag
ord-edfea75450fa4f58a2b05c4761fbe125
Quelldatensatz
uspto-grants-2015_02
Patentnummer
US08946204B2

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