First catalytic enantioselective proton abstraction using chiral aikoxides

Journal of the American Chemical Society

Volumn 118, Issue 49, 1996, Pages 12483-12484

  Amadji, Morad ^a   Vadecard, Jerôme ^a   Plaquevent, Jean Christophe ^a   Duhamel, Lucette ^a   Duhamel, Pierre ^a  

^a UNIVERSITÉ DE ROUEN   (France)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; CYCLOHEXENE DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; REDUCTION; TECHNIQUE;

EID: 0030444308     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960816t     Document Type: Article

References (32)

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20. Prochiral dibrominated dioxanes 1 were prepared according to the following: Amadji, M.; Vadecard, J.; Schimmel, U.; Plé, G.; Plaquevent, J. C. y. Chem. Res., Synop. 1995, 362-363.
21. Vadecard, J. Thesis, University of Rouen, France, 1994.
22. The general experimental procedure is as follows. To a suspension of potassium hydride (2.5 mmol) in THF (8 mL) was added under argon atmosphere a solution of methanol (0.04 mmol) in THF (0.4 mL) at room temperature. After cooling at -80 °C, a solution of compound 1 (1 mmol) and of (1R,2S)-N-methylephedrine 3(H) (0.1 mmol) in THF (2 mL) was added dropwise. The reaction mixture was kept at -80 °C for 3 days. The workup and purification procedure for compounds 2a-e was as follows: the reaction was quenched at -80 °C by aqueous 1 N hydrochloric acid (5 mL). Diethyl ether (5 mL) was then added, and the reaction mixture was allowed to warm to room temperature. After washing three times with aqueous l N hydrochloric acid, the resulting organic solution was neutralized by an aqueous saturated solution of sodium hydrogen carbonate and then dried over magnesium sulfate. After removal of the solvents, the crude material was chromatographed on silica gel 60 (petroleum ether/diethyl ether = 90:10 for compounds 2a-c; petroleum ether/ethyl acetate = 90:10 for compounds 2d,e). The workup and purification procedure for compounds 2f,g was identical except that the use of hydrochloric acid was avoided and that all of the washings were an aqueous saturated solution of sodium hydrogen carbonate. The crude material was chromatographed on silica gel 60 using petroleum ether/ethyl acetate = 90:10 as eluent. The ee values of compounds 2a-c were determined by GC (Supelco β-dex-120). The ee values of compounds 2d-g were determined by HPLC (Chiracel OJ, isopropanol/hexane = 40:60, flow rate = 1 mL/mn).
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