A Practical Route to a Complex Bis-Steroidal Diene Intermediate Using a Microwave Assisted Heck-Reaction

Abstract

A very special set of Heck-conditions led reliably to a non-symmetric bis-steroidal diene which underwent regioselective high-pressure Diels-Alder cycloadditions with non-symmetric electron poor acetylenes. The cyclohexadienes thus obtained were aromatized to the corresponding benzene derivatives.

Key words

natural products - Heck reaction - microwave conditions - Diels-Alder reactions - regioselectivity

References

• 1 Kramer A. Ullmann U. Winterfeldt E. J. Chem. Soc., Perkin Trans. 1  1993,  2865 
• 2 Jautelat R. Müller-Fahrnow A. Winterfeldt E. J. Prakt. Chem.  1996,  338:  695 
• 3 Drögemüller M. Jautelat R. Winterfeldt E. Angew. Chem., Int. Ed. Engl.  1996,  35:  1572 ; Angew. Chem. 1996, 108, 1669
• 4 Drögemüller M. Flessner T. Jautelat R. Scholz U. Winterfeldt E. Eur. J. Org. Chem.  1998,  2811 
• 5 Cheeseman GWH. Cookson RF. In Chemistry of Heterocyclic Compounds   Vol. 35:  Weissberger A., Taylor E. C., John Wiley & Sons; New York: 1979.  p.3 
• 6 Nawasreh M. In Stereoselective Synthesis of Cephalostatin Analogues as anti-Cancer Agents   Dissertation; Hannover: 2000. 
• 7 Behar V. Danishefsky S. J. Am. Chem. Soc.  1993,  115:  7017 
• 8 Hasse-Held M. Hatzis M. Mann J. J. Chem. Soc., Perkin Trans. 1  1992,  2999 
• 9 Hanson JR. Uyanik C. J. Chem. Res.  1998,  221 ; and references therein
• 10 Beletskaya IP. Cheprakov AV. Chem. Rev.  2000,  100:  3009 
• 11 Crimmins MT. Al Awar RS. Vallin JM. Hollis WG. O’Mahony R. Lever JG. Bankaitis-Davis DM. J. Am. Chem. Soc.  1996,  118:  7513 
• 12 Rudloff V. Can. J. Chem.  1965,  4:  2660 
• 13a Grieco PA. Gilman S. Nishizawa N. J. Org. Chem.  1976,  41:  1485 
• 13b Grieco PA. Yokoyama Y. J. Am. Chem. Soc.  1977,  99:  5210 
• 14 Jeffery T. Tetrahedron Lett.  1985,  26:  2667 
• 15 Flessner T. Doye S. J. Prakt. Chem.  1999,  341:  186 
• 16a Loupry A. Petit A. Hamelin J. Texier-Boullet F. Jacquault P. Mathé D. Synthesis  1998,  1213 
• 16b Lidström P. Tierney J. Wathey B. Westman J. Tetrahedron  2001,  57:  9225 
• 17a Vallin KSA. Larhed M. Hallberg A. J. Org. Chem.  2001,  66:  4340 
• 17b

  Vallin, K. S. A.; Zhang, Q.; Curran, D. P.; Larhed, M.; Hallberg, A. Poster displayed at Drug Discovery Technology 2001 Boston.

• 18 Flessner T. Beiträge zur chemischen Diversität der Cephalostatine   Dissertation; Hannover: 1999. 
• 19 Sauer JC. Org. Synth.  1962,  4:  813 
• 20 Osborn JA. Wilkinson G. Inorg. Synth.  1981,  28:  77 
• 21 Barton DHR. Godfrey CRA. Morzycki JW. Motherwell WB. Ley SV. J. Chem. Soc., Perkin Trans. 1  1982,  1947 
• 22a Birch AJ. Williamson DH. Org. React.  1976,  24:  1 
• 22b Djerassi C. Grutzwiller J. J. Am. Chem. Soc.  1966,  88:  4537