Coordination-Mediated Optical Resolution of Carboxylic Acids with O.O'-Dibenzoyltartaric Acid

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 13-14, 1997, Pages 1534-1536

  Mravik, András ^a   Böcskei, Zsolt ^b   Katona, Zoltán ^a   Markovits, Imre ^a   Fogassy, Elemér ^a  

^a BUDAPEST UNIVERSITY OF TECHNOLOGY AND ECONOMICS   (Hungary)

^b Chinoin Pharmaceutical and Chemical Works Ltd   (Hungary)

Author keywords

Carboxylic acids; Chiral recognition; Enantiomeric resolution

Indexed keywords

EID: 0030822099     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199715341     Document Type: Article

References (9)

1. A. Mravik, E. Fogassy, Z. Lepp, Hung. Pat. Appl. P00185 1996; A. Mravik, Z. Lepp, E. Fogassy, Tetrahedron: Asymmetry 1996, 7, 2387-2390.
2. A. Mravik, E. Fogassy, Z. Lepp, Hung. Pat. Appl. P00185 1996; A. Mravik, Z. Lepp, E. Fogassy, Tetrahedron: Asymmetry 1996, 7, 2387-2390.
3. N. K. Kochetkov, A. M. Likhosherstov, V. N. Kulakov, Tetrahedron 1969, 25, 2313-2323.
4. P. C. Bélanger, H. W. R. Williams, Can. J. Chem. 1983, 61, 1383-1386.
5. 2 with all unique reflections (2788 had intensities higher than 2σ(I)). All non-hydrogen atoms were refined anisotropically. Most hydrogen atoms were generated based on geometrical evidence with X-H bond lengths dependant on the chemical nature of X. Some hydrogen-atom positions (for example those belonging to the two water molecules) were taken from difference-Fourier calculations and reinforced by forming hydrogen bonds with proper geometry. R1 = 0.0602, wR2 = 0.1369, GOF =1.095 for those reflections with I>2σ(I). The Flack parameter x = 0.01(2) confirms the absolute configuration (H. D. Flack, Acta Crystallogr. Sect. A 1983, 39, 876-881). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100 266. Copies of the data can be obtained free of charge on application to The Director, CCDC 12 Union Road, Cambridge CB21EZ, UK (fax: int. code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).
6. 2 with all unique reflections (2788 had intensities higher than 2σ(I)). All non-hydrogen atoms were refined anisotropically. Most hydrogen atoms were generated based on geometrical evidence with X-H bond lengths dependant on the chemical nature of X. Some hydrogen-atom positions (for example those belonging to the two water molecules) were taken from difference-Fourier calculations and reinforced by forming hydrogen bonds with proper geometry. R1 = 0.0602, wR2 = 0.1369, GOF =1.095 for those reflections with I>2σ(I). The Flack parameter x = 0.01(2) confirms the absolute configuration (H. D. Flack, Acta Crystallogr. Sect. A 1983, 39, 876-881). Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-100 266. Copies of the data can be obtained free of charge on application to The Director, CCDC 12 Union Road, Cambridge CB21EZ, UK (fax: int. code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).
7. The previously prepared acidic calcium salt or dibenzoyltartaric acid and calcium oxide were dissolved in hot ethanol, and the racemic ester was added. In some cases crystallization can be carried out from this solution, but more frequently from a solvent mixture made by adding further solvents (such as acetone, toluene, or ethyl acetate). However, most of the complexes were separated from an ester-type solvent after the ethanol was removed by evaporation.
8. Characterized by thermoanalytical methods (TGA, EGD), elemental analysis, and ICP-AES. The structure of the complex formed with two molecules of methyl mandelate was determined by X-ray crystallography (A. Mravik, Z. B̈cskei, Z. Katona, I. Markovits, G. Pokol, D. K. Menyhárd, E. Fogassy, Chem. Commun. 1996, 1983-1984.) In some cases partial decomposition occurs at slightly elevated temperatures or even at room temperature. Measurements were performed on air-dried samples, which may contain 0.5-2% of volatile impurities. Furthermore, the relatively high molecular weight may cause uncertainty in the results.
9. 4 alcohols afforded complex salts in which the ee values of the ethyl mandelate were in the range of 31-78%.