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Separation of the enantiomers of substituted dihydrofurocoumarins by HPLC using macrocyclic glycopeptide chiral stationary phases

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Abstract

Enantiomer separations by HPLC using the macrocyclic glycopeptides teicoplanin (Chirobiotic T), teicoplanin aglycon (Chirobiotic TAG), and ristocetin A (Chirobiotic R) chiral stationary phases (CSP) have been achieved on a unique series of potentially biologically active racemic analogues of dihydrofurocoumarin. The macrocyclic glycopeptides have proven to be very selective for this class of compound. All of the 28 chiral analogues examined afforded baseline separation on at least one of the macrocyclic glycopeptide CSP. The teicoplanin CSP showed the broadest enantioselectivity with 24 of the compounds baseline separated. The TAG and the R CSP produced 23 and 14 baseline separations respectively. All three mobile phase modes, i.e. normal phase (NP), reversed phase (RP), and new polar organic modes (PO), have been evaluated. The NP mode proved to be most effective for the separation of chiral dihydrofurocoumarins on all CSP tested. In the reversed phase (RP) mode, all three CSP separated a similar number of compounds. It was observed that the structural characteristics of the analytes and steric effects are very important factors leading to chiral recognition. Hydrogen bonding was found to play a secondary role in chiral discrimination in the normal phase and polar organic modes. Hydrophobic interactions are important for chiral separation in the reversed-phase mode. Chromatographic retention data does not provide information on the absolute configuration of these chiral dihydrofurocoumarin derivatives. However, when coupled with circular dichroism using the exciton coupling chirality method, the enantiomer elution order and the absolute configuration of some chiral dihydrofurocoumarins were successfully determined.

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References

  1. Pathak MA, Kramer DM, Fitzpatrick TB (1973) Sunlight and man. University of Tokyo Press

  2. Regan JD, Parrish JA (1982) The science of photomedicine. Plenum Press, New York

  3. Gasparro EP (1989) Psoralen DNA photobiology. CRC Press, Boca Raton, FL

  4. Guilet D, Helesbeux JJ, Seraphin D, Sevenet T, Richomme P, Bruneton J (2001) J Nat Prod 64:563

    Article  CAS  PubMed  Google Scholar 

  5. Via LD, Gia O, Magno SM, Santana L, Teijeira M, Uriarte E (1999) J Med Chem 42:4405

    Article  PubMed  Google Scholar 

  6. Jasinskas A, Jasinskiene N, Langmore JP (1998) Biochim Biophys Acta 1397:285

    Article  CAS  PubMed  Google Scholar 

  7. Kang SY, Lee KY, Sung SH, Park MJ, Kim YC (2001) J Nat Prod 64:683

    Article  CAS  PubMed  Google Scholar 

  8. Pescitelli NBG, Xiao TL, Rozhkov RV, Larock RC, Armstrong DW (2003) Org Biomol Chem 1:186

    Article  CAS  Google Scholar 

  9. Lee D, Bhat KPL, Fong HHS, Farnsworth NRR, Pezzuto JM, Kinghorn AD (2001) J Nat Prod 64:1286

    Article  CAS  PubMed  Google Scholar 

  10. Beiber RC, Ivie GW, Obertli EH, Holt DL (1983) Food Chem Toxicol 21:163

    Article  PubMed  Google Scholar 

  11. Erdelmeier CAJ, Meier B, Sticher O (1985) J Chromatogr 346:456

    Article  CAS  Google Scholar 

  12. Stermitz FR, Thomas RD (1973) J Chromatogr 77:431

    Article  CAS  PubMed  Google Scholar 

  13. Stanjek V, Miksch M, Boland W (1997) Tetrahedron 53:17699

    Article  CAS  Google Scholar 

  14. Rozhkov R, Larock R (2003) Org Lett 5:797

    Article  CAS  PubMed  Google Scholar 

  15. Armstrong DW, Tang Y, Chen S, Zhou Y, Bagwill C, Chen J-R (1994) Anal Chem 66:1473

    CAS  Google Scholar 

  16. Armstrong DW, Rundlett K, Reid GL III (1994) Anal Chem 66:1690

    CAS  PubMed  Google Scholar 

  17. Armstrong DW, Rundlett KL, Chen J-R (1994) Chirality 6:496

    CAS  PubMed  Google Scholar 

  18. Armstrong DW, Zhou Y (1994) J Liq Chromatogr 17:1695

    CAS  Google Scholar 

  19. Xiao TL, Armstrong DW, Methods in biotechnology, chiral separations—methods and protocols, in press

  20. Armstrong DW (1996) Chimia 50:273

    CAS  Google Scholar 

  21. Gasper MP, Berthod A, Nair UB, Armstrong DW (1996) Anal Chem 68:2501

    Article  CAS  PubMed  Google Scholar 

  22. A Berthod, Y Liu, C Bagwill, DW Armstrong (1996) J Chromatogr A 731:123

    Article  PubMed  Google Scholar 

  23. Armstrong DW (1996) 211th ACS National Meeting, New Orleans, LA, March 24–28, 1996, book of abstracts

  24. Pawlowska M, Armstrong DW (1994) Chirality 6:270

    CAS  PubMed  Google Scholar 

  25. Chen S, Liu Y, Armstrong DW, Borrell JI, Martinez-Teipel B, Matallana JL (1995) Biochim Biophys Acta 1263:2703

    CAS  Google Scholar 

  26. Armstrong DW, Liu Y, Ekborgott KH (1995) Chirality 7:474

    CAS  Google Scholar 

  27. Chen S, Liu Y, Armstrong DW, Borrell JI, Martinez-Teipel B, Matallana JL (1995) J Liq Chromatogr 18:1495

    CAS  Google Scholar 

  28. Ward TJ, Dann CI, Blaylock A (1995) J Chromatogr A 715:337

    Article  CAS  PubMed  Google Scholar 

  29. Nair UB, Chang SSC, Armstrong DW, Rawjee YY, Eggleston DS, McArdle JV (1996) Chirality 8:590

    Article  CAS  Google Scholar 

  30. Berthod A, Nair UB, Bagwill C, Armstrong DW (1996) Talanta 43:1767

    Article  CAS  Google Scholar 

  31. Strege MA, Huff BE, Risely DS (1996) LCGC 14:144

    CAS  Google Scholar 

  32. Ward TJ (1996) LCGC 14:886

    CAS  Google Scholar 

  33. Ekborg-Ott KH, Armstrong DW (1997) Chiral separations: application and technology. chap 9, p 201

    Google Scholar 

  34. Kleidernigg OP, Kappe CO (1997) Tetrahedron Asymmetry 8:2057

    Article  CAS  Google Scholar 

  35. Sharp VS, Risley DS, Mccarthy S, Huff BE, Strege MA (1997) J Liq Chromatogr 20:887

    CAS  Google Scholar 

  36. Torok G, Peter A, Toth G, Tourwe D, Van Den Nest W, Iterbeke K, Armstrong DW (1998) Proc 25th Eur Pept Symp, p 302

  37. Peter A, Torok G, Toth G, Tourwe D, Mannekens E, Van Den Nest W, Sapi J, Armstrong DW (1998) Proc 25th Eur Pept Symp, p 300

  38. Ekborg-Ott KH, Kullman JP, Wang X, Gahm K, He L, Armstrong DW (1998) Chirality 10:627

    Article  CAS  PubMed  Google Scholar 

  39. Peter A, Torok G, Toth G, Van den Nest W, Laus G, Tourwe D, Armstrong DW (1998) Chromatographia 48:53

    CAS  Google Scholar 

  40. Ekborg-Ott K, Liu Y, Armstrong DW (1998) Chirality 10:434

    Article  CAS  PubMed  Google Scholar 

  41. Armstrong DW, Lee JT, Chang LW, Tetrahedron (1998) Asymmetry 9:2043

    Article  CAS  Google Scholar 

  42. Aboul-Enein HY, Serignese V (1999) Chromatographia 13:520

    CAS  Google Scholar 

  43. Aboul-Enein HY, Serignese V (1998) Chirality 10:358

    Article  CAS  Google Scholar 

  44. Joyce KB, Jones AE, Scott RJ, Biddlecombe RA, Pleasance S (1998) Rapid Commun Mass Spectrom 12:1899

    Article  CAS  PubMed  Google Scholar 

  45. Fried KM, Koch P, Wainer IW (1998) Chirality 10:484

    Article  CAS  PubMed  Google Scholar 

  46. Lehotay J, Hrobonová K, Krupcík J, Cizmárik J (1998) Pharmazie 53:863

    CAS  Google Scholar 

  47. Schneiderheinze JM, Armstrong DW, Berthod A (1999) Chirality 11:330

    Article  CAS  PubMed  Google Scholar 

  48. Armstrong DW, He L, Yu T, Lee JT, Liu Y-s (1999) Tetrahedron Asymmetry 10:37

    Article  CAS  Google Scholar 

  49. D'Acquarica I, Gasparrini F, Misiti D, Villani C, Carotti A, Cellamare S, Muck S (1999) J Chromatogr A 857:145

    Article  CAS  PubMed  Google Scholar 

  50. Ramos LM, Bakhtiar R, Majumdar T, Hayes M, Tse F (1999) Rapid Commun Mass Spectrom 13:2054

    Article  CAS  PubMed  Google Scholar 

  51. Tesarova E, Bosakova Z, Zuskova I (2000) J Chromatogr A 879:147

    Article  CAS  PubMed  Google Scholar 

  52. Karlsson C, Karlsson L, Armstrong DW, Owens PK (2000) Anal Chem 72:4394

    Article  CAS  PubMed  Google Scholar 

  53. Berthod A, Chen X, Kullman JP, Armstrong DW, Gasparrini F, D'Acquarica I, Villani C, Carotti A (2000) Anal Chem 72:1767

    Article  CAS  PubMed  Google Scholar 

  54. Peyrin E, Ravelet C, Nicolle E, Villet A, Grosset C, Ravel A, Alary J (2001) J Chromatogr A 923:37

    Article  CAS  PubMed  Google Scholar 

  55. Xiao TL, Zhang B, Lee JT, Hui F, Armstrong DW (2001) J Liq Chromatogr Related Technol 24:2673

    Article  CAS  Google Scholar 

  56. Berthod A, Xiao TL, Liu Y, Jenks WS, Armstrong DW (2002) J Chromatogr A 955:53

    Article  CAS  PubMed  Google Scholar 

  57. Sadek PC (1996) The HPLC solvent guide. Wiley, New York

  58. Seaver C, Przybytek J (1995) LCGC Int 8:190–195 (April 1995)

    Google Scholar 

  59. Burdick and Jackson solvent guide, 3rd edn. Burdick and Jackson, Muskegon, Michigan, USA, 1990

  60. Schneider RL (1975) Physical properties of some organic solvents, Eastman Org Chem Bull, vol 47, no 1

  61. Chang SC, Reid GL, Chen S, Chang CD, Armstrong DW (1993) Trends Anal Chem 12:144

    Article  CAS  Google Scholar 

  62. Armstrong DW, Chen S, Chang C, Chang S (1992) J Liq Chromatogr Related Technol 15:545

    CAS  Google Scholar 

Download references

Acknowledgements

Support of this research by the National Institutes of Health, NIH RO1 GM53825–06, is gratefully acknowledged. R.V.R. and R.C.L. also acknowledge the donors of the Petroleum Research Fund, administered by the American Chemical Society, for partial support of this research and Johnson Matthey Inc., and Kawaken Fine Chemicals Co. Ltd, for donations of palladium acetate.

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Authors and Affiliations

  1. Department of Chemistry, Iowa State University, Ames, IA, 50011, USA

    Tom Ling Xiao, Roman V. Rozhkov, Richard C. Larock & Daniel W. Armstrong

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  1. Tom Ling Xiao
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  2. Roman V. Rozhkov
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  3. Richard C. Larock
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  4. Daniel W. Armstrong
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Correspondence to Daniel W. Armstrong.

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Xiao, T.L., Rozhkov, R.V., Larock, R.C. et al. Separation of the enantiomers of substituted dihydrofurocoumarins by HPLC using macrocyclic glycopeptide chiral stationary phases. Anal Bioanal Chem 377, 639–654 (2003). https://doi.org/10.1007/s00216-003-2110-z

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  • DOI: https://doi.org/10.1007/s00216-003-2110-z

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