Determination of the Relative Configuration of the C-2-C-1′-Fragment of Cytostatin­

Abstract

Four diastereomers of a simple subtructure of cytostatin containing the α,β-unsaturated lactone subunit were synthesized and their NMR-spectroscopical data were compared with values recorded for the natural product in order to unravel the relative stereochemistry in cytostatin.

Key words

natural products - lactones - aldol reactions - asymmetric synthesis - phosphatases

References

• 1 For a review see: Davies-Coleman MT. Galambos J. Hough L. James CE. Khan R. Krohn K. Lonasmaa M. Rivett DEA. In Progress in the Chemistry of Organic Natural Products   Vol. 55:  Herz W. Grisebach H. Kirby GW. Tamm C. Springer-Verlag; New York: 1989.  p.1 
• 2 Amemiya M. Someno T. Sawa R. Naganawa H. Ishizuka M. Takeuchi T. J. Antibiot  1994,  47:  541 
• 3a Brohm D. Metzger S. Bhargava A. Müller O. Lieb F. Waldmann H. Angew. Chem., Int. Ed. Engl.  2002,  41:  307 
• 3b

  Breinbauer, R.-P.; Vetter, I.; Waldmann, H., Angew. Chem., Int. Ed. Engl., accepted

• 3c Zhang Z.-Y. Curr. Opin. Chem. Biol.  2001,  5:  416 
• 4 Bialy L. Waldmann H. Angew. Chem., Int. Ed. Engl.  2002,  41:  1748 
• See for example:
• 5a Entzeroth M. Blackman Mynderse AJ. Moore RE. J. Org. Chem.  1985,  50:  1255 
• 5b Diez-Martin D. Kotecha NR. Ley SV. Mantegani S. Menendez CJ. Organ HM. White AD. Banks BJ. Tetrahedron  1992,  37:  7899 
• 5c Jung ME. Lee CP. Org. Lett.  2001,  3:  333 
• 5d Bluet G. Bazán-Tejeda B. Campagne J.-M. Org. Lett.   2001,  3:  3807 
• 6 Evans DA. Bartroli JA. Shih TL. J. Am. Chem. Soc.  1981,  103:  2127 
• 7 Walker M. Heathcock CH. J. Org. Chem.  1990,  55:  173 
• 8 Evans DA. Bender SL. Morris J. J. Am. Chem. Soc.  1988,  110:  2506 
• 9a Raimundo BC. Heathcock CH. Synlett  1995,  12:  1213 
• 9b Paterson I. Hulme AN. J. Org. Chem.  1995,  60:  3288 
• 10 Penning TD. Djuric SD. Haack RA. Kalish VJ. Myashiro JM. Rowell BW. Yu SS. Synth. Commun.  1990,  20:  307 
• 11 Dess DB. Martin JC. J. Am. Chem. Soc.  1991,  113:  7277 
• 12 Still WC. Gennari C. Tetrahedron Lett  1983,  24:  4405 
• 13 Lee AS.-Y. Hu Y.-J. Chu S.-F. Tetrahedron  2001,  57:  2121 
• 14 Mukayiama T. Inoue T. Chem. Lett.  1976,  559