2-Bromo-3-methyl-2-cyclopenten-1-ol → 2-Ethyl-3-methyl-cyclopent-2-enol

HRID 560077

Reaktionsgleichung

Reaktionsgleichung von HRID 560077
Br[C:2]1[CH:3]([OH:8])[CH2:4][CH2:5][C:6]=1[CH3:7].[CH2:9]([Mg]Br)[CH3:10]>C1COCC1.[Ni](Cl)Cl.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>[CH2:9]([C:2]1[CH:3]([OH:8])[CH2:4][CH2:5][C:6]=1[CH3:7])[CH3:10]

Komponenten

5

Edukt 2

HCID 107497992-Bromo-3-methyl-2-cyclopenten-1-olHCID 178418443HCID 178418443, Verbindung

Produkt 1

HCID 219861782-Ethyl-3-methyl-cyclopent-2-enol

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 2724937Dichloro(1,1'-(1,3-propanediyl)bis(1,1-diphenylphosphine-kappaP))nickelKatalysatorHCID 8028TetrahydrofuranLösungsmittel

Versuchsvorschrift

The alcohol (Intermediate V2, 16 mmol) in THF (30 mL) at 0° C. was treated with ethyl magnesium bromide (40 mmol). The catalyst, 1,3-bis(diphenylphosphino)propane nickel (II) chloride (0.75 mmol) (NiCl2dppp) was added in one portion and the mixture was heated to reflux for 3 hours following the procedure of Organ et al. J. Org. Chem. 1997, 62, 1523, incorporated herein by reference.) The reaction mixture was cooled to rt and quenched with sat. NH4Cl solution. The mixture was filtered and partitioned between brine and diethyl ether. The organic layer was removed and dried over Na2SO4, filtered and concentrated under vacuum. The oil was purified by chromatography on SiO2 with 20% EtOAc:Hx to yield 2-ethyl-3-methyl-cyclopent-2-enol (Intermediate V3). Use of the alcohol (Intermediate V3) in the applicable steps of Method A and Method P produced 4-(2-ethyl-3-methyl-cyclopent-2-enylmethyl)-1,3-dihydro-imidazol-2-one (Compound 64). 1H NMR (300 MHz, CD3OD-d4): δ 6.03 (s, 1H), 2.88 (brs, 1H), 2.65-2.59 (m, 1H), 2.27-1.83 (series of m, 6H), 1.62 (s, 3H), 1.54-1.45 (m, 1H), 0.97 (t, J=6 Hz, 3H).

Aufarbeitung

  1. temperaturethe mixture was heated
  2. temperatureto reflux for 3 hours
  3. customquenched with sat. NH4Cl solution
  4. filtrationThe mixture was filtered
  5. custompartitioned between brine and diethyl ether
  6. customThe organic layer was removed
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. concentrationconcentrated under vacuum
  10. customThe oil was purified by chromatography on SiO2 with 20% EtOAc

Quellen und Nachweise

ORD-Eintrag
ord-a3c16a0b5b07472787913ff29167cdd6
Quelldatensatz
uspto-grants-2011_11
Patentnummer
US08063087B2

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