Reaktion #511375

Reaktionsgleichung

Quinine

cis-5-Norbornene-exo-2,3-dicarboxylic anhydride

toluene

methanol

→

(1S,2S,3R,4R)-3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid

Ausbeute 99.5%

Lösungsmittel

carbon tetrachloride

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigethe flask was degassed
2. 2
   workup.STIRRINGWhile stirring
3. 3
   workup.STIRRINGThe mixture was stirred at −55° C. for 16 h
4. 4
   TemperaturUpon warming to 25° C.
5. 5
   Einengenthe mixture was concentrated in vacuo to a foam
6. 6
   workup.DISSOLUTIONThe foam was dissolved in a mixture of ethyl acetate (400 mL) and 1.0 M aqueous hydrochloric acid solution (400 mL)
7. 7
   SonstigeThe layers were separated
8. 8
   Waschenthe organic layer was further washed with 1.0 M aqueous hydrochloric acid solution (2×200 mL), saturated aqueous brine solution (100 mL)
9. 9
   Trocknendried over magnesium sulfate
10. 10
    Filtrationfiltered
11. 11
    Einengenconcentrated in vacuo

Vorschrift

The starting material (a) was prepared as described in J. Org. Chem. 2000, 65, 6984-6991. cis-5-Norbornene-exo-2,3-dicarboxylic anhydride (5 g, 30.45 mmol) was suspended in a 1:1 mixture of toluene and carbon tetrachloride (610 mL). The mixture was stirred for 10 min. Quinine (10.87 g, 33.5 mmol) was added and the flask was degassed and backfilled with nitrogen. The solution was cooled to −55° C. While stirring, methanol (3.7 mL, 91.35 mmol) was added. The mixture was stirred at −55° C. for 16 h. Upon warming to 25° C., the mixture was concentrated in vacuo to a foam. The foam was dissolved in a mixture of ethyl acetate (400 mL) and 1.0 M aqueous hydrochloric acid solution (400 mL). The layers were separated and the organic layer was further washed with 1.0 M aqueous hydrochloric acid solution (2×200 mL), saturated aqueous brine solution (100 mL) and dried over magnesium sulfate, filtered, and concentrated in vacuo to afford the desired product, (1S,2S,3R,4R)-3-(methoxycarbonyl)bicyclo[2.2.1]hept-5-ene-2-carboxylic acid (5.95 g, 30.3 mmol, 99%), as a clear oil. 1H NMR (400 MHz, DMSO-d6) δ: 1.31 (1H, d, J=8.5 Hz), 1.98 (1H, d, J=8.6 Hz), 2.51 (2H, d, J=1.6 Hz), 2.95 (2H, bs), 3.52 (3H, s), 6.17-6.21 (2H, m), 12.16 (1H, s).

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