Diastereoselective Synthesis of Chiral cis-Annulated Polycyclic Heterocycles from d-Glucose by Domino Knoevenagel-Hetero-Diels-Alder Reaction [1]

Abstract

A new and simple chiral synthesis of cis-annulated polycyclic dihydropyrans 4 and 8 has been achieved by domino Knoe­venagel-hetero-Diels-Alder reactions of O-prenyl derivative of the chiral sugar derived aldehyde 2 with 1,3-dicarbonyl compounds 1 or 6 in MeCN in the presence of a catalytic amount of ethylenediammonium diacetate (EDDA)_. The products are formed with extremely high cis-selectivity in good to excellent yields.

Keywords

domino reaction - Knoevenagel reaction - Diels-Alder reaction - EDDA - diastereoselective

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IICT Communication No 030124.

References

• 2a Ciganek E. Org. React.  1984,  32:  1 
• 2b Taber DF. Intramolecular Diels-Alder and Alder Ene Reactions   Springer Verlag; New York: 1984. 
• 2c Desimoni G. Tacconi G. Chem. Rev.  1975,  75:  851 
• 3a Tietze LF. Brumby T. Pretor M. Remberg G. J. Org. Chem.  1998,  53:  810 
• 3b Tietze LF. Ott C. Haunert F. Can. J. Chem.  2001,  79:  1511 
• 3c Tietze LF. Chem. Rev.  1996,  96:  115 
• 3d Tietze LF. Brumby T. Pretor M. Synthesis  1987,  700 
• 3e Tietze LF. Stegelmeier H. Harms K. Brumby T. Angew. Chem., Int. Ed. Engl.  1982,  21:  863 
• 3f Tietze LF. J. Heterocycl. Chem.  1990,  24:  47 
• 3g Tietze LF. Modi A. Med. Res. Rev.  2000,  20:  304 
• 3h Tietze LF. Haunert F. Domino-Reactions in Organic Synthesis in Stimulating Concepts in Chemistry   Wiley-VCH; Weinheim: 2000.  p.39-64  
• 4a Ceulemans E. Voets M. Emmers S. Dehaen W. Synlett  1997,  1155 
• 4b Ceulemans E. Voets M. Emmers S. Uytterhoeven K. Meervelt LV. Dehaen W. Tetrahedron  2002,  58:  531 
• 5a Tietze LF. Beifuss U. Angew. Chem., Int. Ed. Engl.  1993,  32:  131 
• 5b Tietze LF. Von Kiedrowski G. Berger B. Angew. Chem., Int. Ed. Engl.  1982,  21:  221 
• 6a Waldmann H. Domino Reaction in Organic Synthesis Highlight II   Waldman H. VCH; Weinheim: 1995.  p.193-202  
• 6b Tietze LF. In Selectivity: A Goal for Synthetic Efficiency   Bartmann W. Trott BM. Verlag Chemie; Weinheim: 1984.  p.299 
• 7 Sabitha G. Venkata Reddy E. Yadav JS. Rama Krishna KVS. Ravi Sankar A. Tetrahedron Lett.  2002,  43:  4029 
• 8a Tetrahydrochromano[4,3-b]quinolines: Sabitha G. Venkata Reddy E. Yadav JS. Synthesis  2001,  1979 
• 8b Hexahydrodibenzo[b,h][1,6]naphthyridines: Sabitha G. Venkata Reddy E. Maruthi C. Yadav JS. Tetrahedron Lett.  2002,  43:  1573 
• 8c Octahydroacridines: Sabitha G. Venkata Reddy E. Yadav JS. Synthesis  2002,  409 
• 8d Sabitha G. Srinivas Reddy C. Maruthi C. Venkata Reddy E. Yadav JS. Synth. Commun.  2003,  in press 
• 9 Minimum energy calculations were carried out on a Silicon graphics O₂ workstation, using SYBYL 6.8. Tripos force field with default parameters used throughout the simulations. The structures were energy minimized using Steepest Descent, followed by Conjugate Gradient methods for a maximum of 1000 iterations or RMS deviation of 0.05 kcal mol^-1, whichever was earlier. The derived energy minimized structures were finally normalized geometrically with AM1 algorithm using MOPAC.
• 10a Tietze LF. Fischer R. Angew. Chem., Int. Ed. Engl.  1983,  22:  888 
• 10b Tietze LF. Fischer R. Remberg G. Liebigs. Ann. Chem.  1987,  971 

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IICT Communication No 030124.