Asymmetric synthesis of (R)- and (S)-2-trifluoromethylepinephrine

Tetrahedron Letters

Volumn 45, Issue 13, 2004, Pages 2731-2733

  Dong, Lun Cong ^a   Crowe, Michael ^a   West, Jonathan ^a   Ammann, Jeffrey R ^a  

^a US Army Dental and Trauma Research Detachment   (United States)

Author keywords

Asymmetric synthesis; Epinephrine; Salen catalyst; Trifluoromethylation

Indexed keywords

2 TRIFLUOROMETHYLEPINEPHRINE; 3,4 DIMETHOXY 2 TRIFLUOROMETHYLBENZALDEHYDE; ADRENALIN; BENZALDEHYDE DERIVATIVE; BENZENE DERIVATIVE; CYANOHYDRIN; SILYL CYANOHYDRIN; TITANIUM; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC SYNTHESIS; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CATALYST; CHIRALITY; DRUG FORMULATION; DRUG SYNTHESIS; HIGH PERFORMANCE LIQUID CHROMATOGRAPHY; MELTING POINT; VASOCONSTRICTION;

EID: 1542268879     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2004.02.040     Document Type: Article

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21. 4, and filtered. The solvent was removed in vacuo to afford 3.72 g (15.9 mmol, 25.1%) of 5 as a yellow oil that was used without further purification.
22. In our attempt to optimize the asymmetric synthesis of 6R and 6S, we performed the addition of aldehyde 5 and TMSCN to the catalysts at an elevated temperature (rt) followed by stirring for 18 h. Reduction of the silyl cyanohydrins 6R and 6S yielded moderate to poor ee of β-aminoethanols 7R and 7S.
23. 1H NMR, most likely due to slow rotation around the CO-N bond. The ratio of s-cis to s-trans for each enantiomer was ~4:1 using the benzylic proton as the integration indicator. The detection of monosubstituted formamide isomers by NMR is noted in: Pretsch E., Clerc T., Seibl J., Simon W. Fresenius W., Huber J.F.K., Pungor E., Rechnitz G.A., Simon W., West T.S. Tables of Spectral Data for Structure Determination of Organic Compounds. 2nd ed. 1989;H155 Springer, Berlin.
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25. 4 (pH=4, 100 mM) at a flow of 1 mL/min. The absolute configuration of 1R and 1S was determined by comparison of the elution order of authentic (R)-epinephrine and racemic epinephrine using identical chiral HPLC conditions.