Download PDF
Synthesis 2011(4): 674-680  
DOI: 10.1055/s-0030-1258401
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Stereoselective Synthesis of Spiro Tricyclic Polyoxygenated Compounds: Solvolytic Behavior of 1-(Tosyloxymethyl)spiro[2.4]hepta-4,6-diene

Céline Reynauda, Michel Giorgib, Henri Doucet*c, Maurice Santelli*a
a Laboratoire Chimie Provence, associé au CNRS, UMR 6264, Faculté des Sciences de Saint Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Fax: +33(4)91288758; e-Mail: m.santelli@univ-cezanne.fr;
b Spectropôle, Faculté des Sciences de St-Jérôme, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
c Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes ‘Catalyse et Organometalliques’, Campus de Beaulieu, 35042 Rennes, France
Fax: +33(2)23236939; e-Mail: henri.doucet@univ-rennes1.fr;
Further Information

Publication History

Received 7 October 2010
Publication Date:
12 January 2011 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

The Diels-Alder reaction of spirobicyclic cyclopentadiene derivatives, prepared by reaction of cyclopentadienyllithium and epichlorohydrin, with maleic anhydride gave a simple access to spiro tricyclic polyoxygenated compounds of synthetic interest. The solvolytic behavior of 1-(tosyloxymethyl)spiro[2.4]hepta-4,6-diene, a 5-spirocyclopentadiene, shows that the ionization of the tosylate was unlikely.

Key words

tricyclic compounds - Diels-Alder reaction - spiro compounds - stereoselective synthesis

    References

  • 1a Laurenti D. Feuerstein M. Pèpe G. Doucet H. Santelli M. J. Org. Chem.  2001,  66:  1633 
    Search in Google Scholar
  • 1b Doucet H. Santelli M. Synlett  2006,  2001 
  • 2 Reynaud C. Fall Y. Feuerstein M. Doucet H. Santelli M. Tetrahedron  2009,  65:  7440 
    CrossrefSearch in Google Scholar
  • 3a Bangert K. Boekelheide V. Tetrahedron Lett.  1963,  4:  1119 
    Search in Google Scholar
  • 3b Corey EJ. Shiner CS. Volante RP. Cyr CR. Tetrahedron Lett.  1975,  16:  1161 
    Search in Google Scholar
  • 3c Lokensgard DM. Dougherty DA. Hilinski EF. Berson JA. Proc. Natl. Acad. Sci. U.S.A.  1980,  77:  3090 
    Search in Google Scholar
  • 3d Attah-Poku SK. Gallacher G. Ng AS. Taylor LEB. Alward SJ. Fallis AG. Tetrahedron Lett.  1983,  24:  677 
    Search in Google Scholar
  • 3e Gallacher G. Ng AS. Attah-Poku SK. Antczak K. Alward SJ. Kingston JF. Fallis AG. Can. J. Chem.  1984,  62:  1709 
    Search in Google Scholar
  • 3f González AG. Darias J. Díaz F. Tetrahedron Lett.  1984,  25:  2697 
    Search in Google Scholar
  • 3g Antczak K. Kingston JF. Fallis AG. Can. J. Chem.  1985,  63:  993 
    Search in Google Scholar
  • 3h Antczak K. Kingston JF. Fallis A. Hanson AW. Can. J. Chem.  1987,  65:  114 
    Search in Google Scholar
  • 3i Ledford BE. Carreira EM. J. Am. Chem. Soc.  1995,  117:  11811 
    Search in Google Scholar
  • 3j Starr JT. Baudat A. Carreira EM. Tetrahedron Lett.  1998,  39:  5675 
    Search in Google Scholar
  • 3k Starr JT. Koch G. Carreira EM. J. Am. Chem. Soc.  2000,  122:  8793 
    Search in Google Scholar
  • 3l Gorman JST. Lynch V. Pagenkopf BL. Young B. Tetrahedron Lett.  2003,  44:  5435 
    Search in Google Scholar
  • 3m Avilov DV. Malusare MG. Arslancan E. Dittmer DC. Org. Lett.  2004,  6:  2225 
    Search in Google Scholar
  • 3n Nadany AE. Mckendrick JE. Tetrahedron Lett.  2007,  48:  4071 
    Search in Google Scholar
  • 5 Frisch MJ. Trucks GW. Schlegel HB. Scuseria GE. Robb MA. Cheeseman JR. Montgomery JA. Vreven T. Kudin KN. Burant JC. Millam JM. Iyengar SS. Tomasi J. Barone V. Mennucci B. Cossi M. Scalmani G. Rega N. Petersson GA. Nakatsuji H. Hada M. Ehara M. Toyota K. Fukuda R. Hasegawa J. Ishida M. Nakajima T. Honda Y. Kitao O. Nakai H. Klene M. Li X. Knox JE. Hratchian HP. Cross JB. Bakken V. Adamo C. Jaramillo J. Gomperts R. Stratmann RE. Yazyev O. Austin AJ. Cammi R. Pomelli C. Ochterski JW. Ayala PY. Morokuma K. Voth GA. Salvador P. Dannenberg JJ. Zakrzewski VG. Dapprich S. Daniels AD. Strain MC. Farkas O. Malick DK. Rabuck AD. Raghavachari K. Foresman JB. Ortiz JV. Cui Q. Baboul AG. Clifford S. Cioslowski J. Stefanov BB. Liu G. Liashenko A. Piskorz P. Komaromi I. Martin RL. Fox DJ. Keith T. Al-Laham MA. Peng CY. Nanayakkara A. Challacombe M. Gill PMW. Johnson B. Chen W. Wong MW. Gonzalez C. Pople JA. Gaussian 03, Revision E.01   Gaussian Inc.; Wallingford (CT): 2004. 
  • 6 Saunders J. Tipney DC. Robins P. Tetrahedron Lett.  1982,  23:  4147 
    CrossrefSearch in Google Scholar
  • 7a Coxon JM. McDonald DQ. Tetrahedron Lett.  1992,  33:  651 
    Search in Google Scholar
  • 7b Werstiuk NH. Ma J. Macaulay JB. Fallis AG. Can. J. Chem.  1992,  70:  2798 
    Search in Google Scholar
  • 7c For recent studies and references, see: Ishida M. Itakura M. Tashiro H. Tetrahedron Lett.  2008,  49:  1804 
    Search in Google Scholar
  • 9 Oda M. Breslow R. Tetrahedron Lett.  1973,  14:  2537 
    CrossrefSearch in Google Scholar
  • 10 Warrener RN. Harrison PA. Sterns M. Russell RA. J. Chem. Soc., Chem. Commun.  1984,  546 
  • 11a Kornblum N. Jones WJ. Anderson GJ. J. Am. Chem. Soc.  1959,  81:  4113 
    Search in Google Scholar
  • 11b Smith MB. March J. March’s Advanced Organic Chemistry   6th ed.:  Wiley; Hoboken (NJ): 2007.  p.1765 
    Search in Google Scholar
  • 12 The silver-assisted solvolysis of cyclopentadien-5-yl iodide is at least 105 times slower than that of cyclopentyl iodide, see: Breslow R. Hoffman JM. J. Am. Chem. Soc.  1972,  94:  2110 
    CrossrefSearch in Google Scholar
  • 13 de Vries EFJ. Brussee J. van der Gen A. J. Org. Chem.  1994,  59:  7133 
    CrossrefSearch in Google Scholar
4

For example, for syn-isomers 2a and 2c, the chemical shifts of carbon atoms of anhydrides are different, and for anti-isomers 3a and 3c the chemical shifts are identical.

8

Special Issue: Nonclassical Carbocations, Acc. Chem. Res. 1983, 16, 425

14

X-ray crystallography: CCDC-794286 (for 3b), contain the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 (1223)336033; or e-mail: deposit@ccdc.cam.ac.uk].