Lithium borohydride → (1S,2R,3R,4S)-3,4-Bis(hydroxymethyl)-2-(2-methylphenyl)cyclohexanol

HRID 1644775Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1644775
[OH:1][C@H:2]1[CH2:7][CH2:6][C@H:5]([C:8](OCC)=[O:9])[C@@H:4]([C:13](OCC)=[O:14])[C@@H:3]1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24].[Li+].[BH4-]>C1COCC1>[OH:14][CH2:13][C@@H:4]1[C@@H:5]([CH2:8][OH:9])[CH2:6][CH2:7][C@H:2]([OH:1])[C@H:3]1[C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][C:19]=1[CH3:24]

Komponenten

4

Edukt 2

HCID 4148881Lithium borohydrideHCID 66774775Diethyl(1S,2S,3R,4S)-3-(2-methylphenyl)-4-hydroxycyclohexane-1,2-dicarboxylate

Produkt 1

HCID 66774537(1S,2R,3R,4S)-3,4-Bis(hydroxymethyl)-2-(2-methylphenyl)cyclohexanolAusbeute 90,9 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel

Reaktionsbedingungen

Temperatur
75 °C

Versuchsvorschrift

To a solution of diethyl (1S,2S,3R,4S)-4-hydroxy-3-(2-methylphenyl)cyclohexane-1,2-dicarboxylate (Step G, 64.1 g, 192 mmol) in 250 mL THF under nitrogen atmosphere was slowly added LiBH4 powder (16.7 g, 767 mmol, excess) at 0° C. The resulting mixture was heated at 75° C. for 12 hr then cooled to RT. The reaction mixture was carefully quenched by addition of 30 mL water at 0° C., then 30 mL 2 N hydrochloric acid. The organic layer was separated and the aqueous was extracted with EtOAc. The combined organic extracts were washed with aqueous NaHCO3, dried over Na2SO4, filtered and the solvent evaporated under vacuum to give 43.7 g of the crude title compound which was used without further purification. 1H-NMR (CDCl3): δ: 7.30-7.13 (4H, m), 3.93-3.68 (3H, m), 3.53 (1H, dd, J1=11.2 Hz, J2=2.3 Hz), 3.27 (1H, dd, J1=11.2 Hz, J2=5.1 Hz), 2.85 (1H, t, J=10.5 Hz), 2.39 (3H, s), 2.19 (1H, m), 1.86 (3H, bs), 1.67 (2H, m), 1.55 (1H, m), 1.45 (1H, m).

Aufarbeitung

  1. customat 0° C
  2. temperaturethen cooled to RT
  3. customThe reaction mixture was carefully quenched by addition of 30 mL water at 0° C.
  4. customThe organic layer was separated
  5. extractionthe aqueous was extracted with EtOAc
  6. washThe combined organic extracts were washed with aqueous NaHCO3
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customthe solvent evaporated under vacuum

Quellen und Nachweise

ORD-Eintrag
ord-14bc70c667fd4cf9bae7b7a2529b5201
Quelldatensatz
uspto-grants-2012_02
Patentnummer
US08124633B2

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