A Regioselective Synthesis of Genistein 4’-O-Ribofuranosides

Abstract

A direct glycosylation reaction of biologically significant isoflavone, genistein (1) with 1,2,3,5-tetra-O-acetyl-β-d-ribofuranose (2) in the presence of tin tetrachloride gave a satisfactory yield of a mixture of 4’-O-α- (3a) and 4’-O-β-d-ribofuranosides (3b), in the ratio 1:2 respectively. After deacetylation, anomers 4a and 4b were separated by chromatographic means. The results are compared with ribosylation of phenol and the regio- and stereoselectivity of genistein glycosylation are discussed.

Key words

bioorganic chemistry - isoflavones - genistein O-glycosides - O-ribosylation - regioselectivity of glycosylation

References

• 1 Haslam E. Structure to Molecular Recognition and Physiological Action: Practical Poliphenolics   Cambridge University Press; Cambridge: 1999. 
• 2 The Handbook of Natural Flavonoids   Vol. 1 & 2:  Harborne JB. Baxter H. J. Wiley & Sons; Chichester, New York, Weinheim, Brisbane, Singapore, Toronto: 1986. 
• 3 Price KR. Fenwick GR. Food Addit. Contam.  1985,  2:  73 
• 4 Hendrich S. Lee K.-W. Xu X. Wang H.-J. Murphy PA. J. Nutr.  1994,  124:  1789s 
• 5 Grynkiewicz G. Achmatowicz O. Pucko W. Herba. Polon.  2000,  46:  151 
• 6 Begona RLM. Moham AR. Papanga G. Miller NJ. Bolwell GP. Rice-Evans CA. Free Radical Res.  1997,  26:  63 
• 7 Tikkanen MJ. Wähälä K. Ojala S. Vihma V. Adlercreutz H. Proc. Natl. Acad. Sci. USA  1998,  95:  3106 
• 8 Lewis PT. Wähälä K. Oikkala A. Mutikainnen I. Meng Q.-H. Adlercreutz H. Tikkanen MJ. Tetrahedron  2000,  56:  7805 
• 9 Samman S. Lyons-Wall PM. Cook NC. Naghi MR. J. Clin. Biochem. Nutr.  1996,  20:  173 
• 10 Nestel PJ. Yamashita T. Sasahara T. Pomeroy S. Dart A. Komesaroff P. Owen A. Abbey A. Arterioscl. Throm.Vas.  1997,  17:  3392 
• 11 Adlercreutz H. Yaghoob M. Höckerstedt K. Acta Oncol.  1992,  31:  115 
• 12 Shibuya Y. Tahara S. Kimura Y. Mizutani J. Z. Naturforsch.  1991,  46c:  513 
• 13 Barnes S. Kirk M. Coward L. J. Agric. Food Chem.  1994,  42:  2466 
• 14 Coward L. Barnes NC. Setchell KDR. Barnes S. J. Agric. Food Chem.  1993,  41:  1961 
• 15 Wang H.-J. Murphy PA. J. Agric. Food Chem  1994,  42:  1666 
• 16 Zemplén G. Farkas L. Chem. Ber.  1943,  76:  1110 
• 17 Lewis P. Kaltia S. Wähälä K. J. Chem. Soc. Perkin Trans. 1  1998,  2481 
• 18 Lewis PT. Wähälä K. Tetrahedron Lett.  1998,  39:  9559 
• 19 Niedballa U. Vorbrüggen H. J. Org. Chem.  1974,  39:  3654 
• 20 Niewczyk A. Krzyzaniak A. Barciszewski J. Markiewicz WT. Nucleos. Nucleot.  1991,  10:  635 
• 21 Aitken DJ. Alijah R. Onyiriuka SO. Suckling CJ. Wood HCS. Zhu L. J. Chem. Soc. Perkin Trans. 1  1993,  597 
• 22 Kazimierczuk Z. Cottam HB. Revankar GR. Robins RK. J. Am. Chem. Soc.  1984,  106:  6379 
• 23 Baker BR. Schaub RE. Kissman HM. J. Am. Chem. Soc.  1955,  77:  5911 
• 24 Boryski J. Nucleos. Nucleot.  1996,  15:  771