Synthesis of Tetrahydrofurans through a Novel Pseudo-meso-trick

Abstract

Diastereoselective synthesis of trisubstituted tetrahydrofuran (d-lyxo-4) from the equimolar diastereomeric mixture of d-erythro- /d -threo-1-pentenitols (1) is described. The synthesis exploits a sequence of two novel reactions: diastereospecific palladium(II)-catalyzed bicyclization of pentenitols 1 with degeneration of the allylic stereogenic center and subsequent regioselective ring-opening of bicyclic skeleton 2.

Key words

palladium - catalysis - stereoselective synthesis - cyclizations - diastereoselectivity

References

• 1a Barlett PA. In Selectivity - A Goal for Synthetic Efficiency   Bartmann W. Trost BM. Verlag Chemie; Weinheim: 1984.  p.1 
• 1b Boivin TL. Tetrahedron  1987,  43:  3309 
• 1c Suh H. Wilcox CS. J. Am. Chem. Soc.  1988,  110:  470 
• 1d Nishiyma S. Shizuri Y. Yamamura S. Tetrahedron Lett.  1985,  26:  6239 
• 1e McLaughlin JL. Chang C.-J. Smith DL. Studies in Natural Products Chemistry   Vol. 9:  Rahman A.-U. Elsevier; Amsterdam: 1991.  p.383 
• 1f McLaughlin JL. Chang C.-J. Smith D.-L. In Human Medicinal Agents From Plants   Kinghorn AD. Balandrin MF. ACS; Washington DC: 1993.  p.112 
• 1g Howard BH. Raistrick H. Biochem. J.  1949,  44:  227 
• 1h Cao S.-G. Wu X.-H. Sim K.-Y. Tan BKH. Pereira JT. Goh S.-H. Tetrahedron  1998,  54:  2143 
• 2a Gracza T. Jäger V. Synlett  1992,  191 
• 2b Gracza T. Jäger V. Synthesis  1994,  1359 
• 2c Dixon DJ. Ley SV. Gracza T. Szolcsányi P. J. Chem. Soc., Perkin Trans. 1  1999,  839 
• 2d Szolcsányi P. Gracza T. Koman M. Pronayová N. Liptaj T. Chem. Commun.  2000,  471 
• 2e Szolcsányi P. Gracza T. Koman M. Pronayová N. Liptaj T. Tetrahedron: Asymmetry  2000,  2579 
• 2f Babjak M. Kapitán P. Gracza T. Tetrahedron Lett.  2002,  43:  6983 
• 2g Babjak M. Kapitán P. Gracza T. Tetrahedron  2005,  61:  2471 
• 3a Jäger V. Gracza T. Dubois E. Hasenöhrl T. Hümmer W. Kautz U. Kirschbaum B. Lieberknecht A. Remen L. Shaw D. Stahl U. Stephan O. In Organic Synthesis via Organometallics, OSM5   Helmchen G. F. Vieweg & Sohn Verlagsgesellschaft; Braunschweig, Wiesbaden: 1997.  p.321 
• 3b Gracza T. Hasenöhrl T. Stahl U. Jäger V. Synthesis  1991,  1108 
• 4 Bravo F. Castillón S. Eur. J. Org. Chem.  2001,  507 
• 5a Cardillo G. Orena M. Tetrahedron  1990,  46:  3321 
• 5b Orena M. In Houben-Weyl   4th ed., Vol. E21e:  Helmchen G. Hoffmann R. Mulzer J. Thieme; Stuttgart: 1995.  p.4760 
• 6 Babjak M. Zálupsk P. Gracza T. ARKIVOC  2005,  v:  45 
• 7 Crotti P. Di Bussolo V. Favero L. Gozzi C. Pineschi M. Tetrahedron: Asymmetry  1997,  8:  1611 
• 8 Kuszmann J. Carbohydr. Res.  1985,  142:  71 
• 9 Olah GA. Narang SC. Balaram Gupta GB. Malhotra R. J. Org. Chem.  1979,  44:  1247