Enzymatic synthesis of enantiomerically pure 1,2-fluorocyclopentanols and 1,2-aminofluorocyclopentanes
DOI:
https://doi.org/10.15407/dopovidi2019.07.066Keywords:
aminofluorocyclopentanes, biocatalysis, fluorocyclopentanols, Kazlauskas rule, lipase Burkholderia cepacia, stereochemistryAbstract
Vicinal fluorocyclopentanol are valuable chiral synthetic blocks for the preparation of a number of natural and synthetic biologically active substances Racemic cis-2-fluorocyclopentanols were separated into enantiomers by the kinetically controlled transesterification with vinyl acetate in the presence of lipases in organic media, High enantioselectivity (ee > 98 %) and good yields of compounds were obtained for all substrates using Burkholderia cepacia lipase, The fluorocyclopentanols were converted into enantiomerically pure 1,2-aminofluorocyclopentanes using the Mitsunobu reaction, The enantiomeric purity of the compounds was determined by Mosher's acid derivatization method, and the absolute configurations were determined using the Kazlauskas rule.
Downloads
References
Eliel, E. L., Wilen, S. H.& Mander, L. N. (1994). Stereochemistry of organic compounds. Wiley: New York.
Sate, T., Gotoh, Y., Watanabe, M. & Fujisawa, T. (1983). Stereoselective total synthesis of (4s)-trans-β-elemenone from (S)-2-cyclopenten-1-ol. Chem. Lett., No. 10, pp. 1533-1536. doi: https://doi.org/10.1246/cl.1983.1533
Hayes, R. & Wallace, T. W. (1990). A simple route to methyl 5S-(benzoyloxy)-6-oxopentanoate, a key intermediate in leukotriene synthesis. Tetrahedron Lett., 31, No. 10, pp. 3355-3356. doi: https://doi.org/10.1016/S0040-4039(00)89063-2
Sabol, J. S. & Cregge, R. J. (1989). Conformationally restricted leukotriene antagonists. Asymmetric synthesis of some nor-leukotriene D4 analogs, Tetrahedron Lett., 30, No. 26, 3377. doi: https://doi.org/10.1016/S0040-4039(00)99249-9
Hu, Q.-Y., Rege, P. D. & Corey, E. J. (2004). Simple, catalytic enantioselective syntheses of estrone and desogestrel. J. Am. Chem. Soc., 126, No. 19, pp. 5984-5986. doi: https://doi.org/10.1021/ja048808x
Kolodiazhna, O. O., Kolodiazhna, A. O. & Kolodiazhnyi, O. I. (2013). Enzymatic preparation of (1S,2R)- and (1R,2S)-stereoisomers of 2-halocyclopentanols. Tetrahedron: Asymmetry, 24, No. 1, pp. 37-42. doi: https://doi.org/10.1016/j.tetasy.2012.11.011
Haufe, G. & Bruns, S. (2002). (Salen)chromium complex mediated asymmetric ring opening of meso- and racemic epoxides with different fluoride sources. Adv. Synth. Catal., 344, No. 2, pp. 165-171. doi: https://doi.org/10.1002/1615-4169(200202)344:2<165::AID-ADSC165>3.0.CO;2-1
Wolker, D. & Haufe, G. (2002). Synthesis of optically active vicinal fluorohydrins by lipase-catalyzed deracemization. J. Org. Chem., 67, No. 9, pp. 3015-3021. doi: https://doi.org/10.1021/jo016331r
Honig, H. & Seufer-Wasserthal, P. (1990). General method for the separation of enantiomeric trans-2-substituted cyclopentanols. Synthesis, No. 12, pp. 1137-1140. doi: https://doi.org/10.1055/s-1990-27115
Dale, J. A. & Mosher, H. S. (1973). Nuclear magnetic resonance enantiomer regents, Configurational correlations via nuclear magnetic resonance chemical shifts of diastereomeric mandelate. O-methylmandelate, and alpha,-methoxy-alpha-trifluoromethylphenylacetate (MTPA) esters. J. Am. Chem. Soc., 95, No. 2, pp. 512-519. doi: https://doi.org/10.1021/ja00783a034
Kazlauskas, R. J., Weissfloch, A., N. E., Rappaport, A. T. & Cuccia, L. A. (1991). A rule to predict which enantiomer of a secondary alcohol reacts faster in reactions catalyzed by cholesterol esterase, lipase from Pseudomonas cepacia, and lipase from Candida rugose. J. Org. Chem., 56, No. 10, pp. 2656-2665. doi: https://doi.org/10.1021/jo00008a016
Parker, D. (1991). NMR determination of enantiomeric purity. Chem. Rev., 91, 7, pp. 1441-1457. doi: https://doi.org/10.1021/cr00007a009
Ohtani, I., Kusumi, T., Kashman, Y. & Kakisawa, H. (1991). High-field FT NMR application of Mosher’s method. The absolute configurations of marine terpenoids. J. Am. Chem. Soc., 113, No. 11, pp. 4092-4096. doi: https://doi.org/10.1021/ja00011a006
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2024 Reports of the National Academy of Sciences of Ukraine
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.
