Reaktion #2642

ord-fcb0d5dcdda04901928d4fd9c09849c7

Reaktionsgleichung

[Na+].[OH-]
sodium hydroxide
[Al+3].[H-].[H-].[H-].[H-].[Li+]
lithium aluminum hydride
[I-].[Li+]
lithium iodide
O=C1C=CC(OC2CCCCO2)C1
4-(tetrahydro-pyran-2-yloxy)-cyclopent-2-enone
O[C@@H]1C=C[C@H](OC2CCCCO2)C1
title compound
Ausbeute 73.5%
O[C@@H]1C=C[C@H](OC2CCCCO2)C1
cis-4-(tetrahydro-pyran-2-yloxy)-cyclopent-2-enol
Ausbeute 73.5%

Reaktionsbedingungen

Detaillierte Bedingungen
See reaction.notes.procedure_details.

Aufarbeitung

  1. 1
    FiltrationThe slurry is filtered
  2. 2
    Sonstigethe resulting phases separated
  3. 3
    ExtraktionThe aqueous phase is extracted with ethyl acetate (2×10 mL)
  4. 4
    Trocknendried over magnesium sulfate
  5. 5
    Filtrationfiltered
  6. 6
    Einengenconcentrated under vacuum
  7. 7
    SonstigeThe crude oil is then purified by chromatography (silica gel, 30 g, 50% ethyl acetate/hexane, 400 mL)

Vorschrift

A slurry of lithium aluminum hydride (222 mg, 5.8 mmol), lithium iodide (3.2 g, 24 mmol), tert-butyl methyl ether (6 mL) and toluene (16 mL) is cooled to -15° C. A solution of 4-(tetrahydro-pyran-2-yloxy)-cyclopent-2-enone (2.179 g, 11.97 mmol, prepared in example 5) in tert-butyl methyl ether (2 mL) and toluene (2 mL) is added dropwise over 40 minutes. The reaction mixture is allowed to stir for 30 minutes. Then sodium hydroxide (1N, 5 mL) is added slowly to the reaction mixture. The slurry is filtered and the resulting phases separated. The aqueous phase is extracted with ethyl acetate (2×10 mL). The organic extracts are combined with the organic phase, dried over magnesium sulfate, filtered and concentrated under vacuum. The crude oil is then purified by chromatography (silica gel, 30 g, 50% ethyl acetate/hexane, 400 mL) to provide the title compound (1.62 g, 73%), cis/trans/1-2+1-4 addition, 88/8/4; 1H NMR (CDCl3) δ6.1 (m, 1H), 4.7 (m, 1H), 4.6 (m, 2H), 3.9 (m, 1H), 3.5 (m, 1H), 2.7 (m, 1H), 1.4-2.0 (m, 8H); 13C NMR (CDCl3) δ 137.2,137.1, 134.8, 133.6, 98.3, 97.8, 79.7, 79.5, 74.7, 74.5, 62.6, 62.5, 42.0, 41.1, 31.1, 30.9, 25.4, 19.6, 19.5; IR (neat) νmax 2944, 2870, 2855, 1723, 1348, 1202, 1182, 1152, 1128, 1078, 1032 cm-1 ; MS (CI) m/e (% relative intensity) 183 (M+H+, 7), 167 (M+H+ -H2O, 40), 85(100).

Quelle

DOI: 10.6084/m9.figshare.5104873.v1Patent: US05728899uspto-grants-1998_03