Dimolybdenum Method for Determination of the Absolute Configuration of vic-Diols - Foundations and Developments

• Autorzy: Górecki M. , Kamińska A. , Ruśkowska P. , Suszczyńska A. , Frelek J.
• Konferencja: 21st Conference on Isoprenoids, 23-29 September 2005, Białystok-Białowieża, Poland
• Języki publikacji: EN

Abstrakty

EN

A straightforward and versatile method for the determination of the absolute configuration of vic-diols is presented. The proposed method involves the in situ formation of chiral complexes of optically active vic-diols with the achiral dimolybdenum tetraacetate [Mo2(OAc)4] acting as an auxiliary chromophore. The resulting CD spectra are suitable for the assignment of absolute configuration, since the observed sign of Cotton effects arising within the d-d absorption bands of the metal cluster depends solely upon the chirality of the 1,2-diol ligands.An empirically based rule correlating a positive/negative helicity expressed by the O-C-C-O torsional angle with the sign of Cotton effects occurring in the 400-280 nm spectral range has been presented. The applicability of the rule is extended to sterically hindered sec/tert vic-diols.

Słowa kluczowe

EN

absolute configuration; circular dichroism; transition metal complexes; chiral Mo complexes

• Wydawca: Polskie Towarzystwo Chemiczne
• Czasopismo: Polish Journal of Chemistry
• Rocznik: 2006
• Tom: Vol. 80, nr 4
• Strony: 523--534
• Opis fizyczny: Bibliogr. 13 poz.

Twórcy

autor

Górecki M.

autor

Kamińska A.

autor

Ruśkowska P.

autor

Suszczyńska A.

autor

Frelek J.

• Institute of Organic Chemistry of the Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, Poland

Bibliografia

• l. CreelmanR.and Mullet J., Plant Cell,9, 1211 (1997).
• 2. Thadepalli H., Chuah S.K., Iskandar L. and Gollapudi S., Int. J. Antimicrob., 20, 180 (2002).
• 3. Somlo M., Reid R.A. and Krupa M., Biochem. J., 162, 51 (1977); Korystov Y.N., Kublik L.N., Kudryavtsev A.A., Levitman M.K., Shaposhnikova V.V., Drinyaev V.A., Mosin V.A., Kruglyak E.B., Sterlina T.S. and Chailakhyan L.M., Doklady Biol. Sci., 392, 475 (2003); Nakakita Y., Nakagawa M. and Sakai H.E., J. Antibiot., 33, 514 (1980).
• 4. Roush W.R., Hartz R.A. and Gustin D.J., J. Am. Chem. Soc., 121, 1990 (1999).
• 5. Frelek J., Perkowska A., Snatzke G., Tima M., Wagner U. and Wolf T H. P., Spectrosc. Mer. J., 2, 274 (l 983); Frelek J., Majer Z., Perkowska A., Snatzke G., Vlahov I., and Wagner U., Pure & Appl. Chem.,57,441(1985).
• 6. Frelek J., Geiger M. and Yoelter W, Current Org. Chem., 3, 145 (1999); Frelek J., Klimek A. and Ruśkowska P., Curr. Org. Chem,. 7, 1081 (2003).
• 7. Cotton F.A. and Watson R.A., Multiple Bonds Between Metal Atoms, Second edition, Clarenden Press-Oxford 1993, pp. 139-243.
• 8. Snatzke G., Angew. Chem. Int. Ed. Engl., 18, 363 (1979).
• 9. Liptak A., Frelek J., Snatzke G. and Vlahov I., Carbohydr. Res., 164, 149 (1987).
• 10. Snatzke G., in Optical Activity and Chiral Discrimination, D. Reidel Publishing Company, Dordrecht,Boston, London 1979, p. 30.
• 11. Polavarapu P.L., J. Phys. Chem. A, 105, 6991 (2001).
• 12. Frelek J. and Snatzke G., Fresenius' Z. Anal. Chem., 316, 261 (1983).
• 13. Gawronski J. and Skowronek P., Curr. Org. Chem., 8, 65 (2004); Superchi S., Casarini D., Summa C.and Rosini C., J. Org. Chem., 69, 1685 (2004).