Synthesis of Methylene Exoglycals Using a Modified Julia Olefination

 

 Buy Article Permissions and Reprints All articles of this category

Abstract

A new route to exomethylene sugars is reported. The use of a two-step coupling-elimination procedure allows successful Julia olefination of sugar-derived lactones.

References

• 1 Taillefumier C. Chapleur Y. Chem. Rev.  2004,  104:  263 
  CrossrefGoogle Scholar
• 2a Brockhaus M. Lehmann J. Carbohydr. Res.  1977,  53:  21 
  CrossrefGoogle Scholar
• 2b Lehmann J. Schwesinger B. Carbohydr. Res.  1982,  107:  43 
  CrossrefGoogle Scholar
• 3a Nicotra F. Panza L. Russo G. Tetrahedron Lett.  1991,  32:  4035 
  Google Scholar
• 3b Gervay J. Flaherty TM. Holmes D. Tetrahedron  1997,  53:  16355 
  Google Scholar
• 3c Faivre-Buet V. Eynard I. Nga HN. Descotes G. Grouiller A. J. Carbohydr. Chem.  1993,  12:  349 
  Google Scholar
• 4a Rajanbabu TV. Reddy GS. J. Org. Chem.  1986,  51:  5458 
  CrossrefGoogle Scholar
• 4b Lay L. Nicotra F. Panza L. Russo G. Caneva E. J. Org. Chem.  1992,  57:  1304 
  CrossrefGoogle Scholar
• 4c Rubinstein G. Mallet JM. Sinaӱ P. Tetrahedron Lett.  1998,  39:  3697 
  CrossrefGoogle Scholar
• 5 Wilcox CS. Long GW. Suh H. Tetrahedron Lett.  1984,  25:  395 
  CrossrefGoogle Scholar
• 6a Martin OR. Xie F. Carbohydr. Res.  1994,  264:  141 
  CrossrefGoogle Scholar
• 6b Vidal T. Haudrechy A. Langlois Y. Tetrahedron Lett.  1999,  40:  5677 
  CrossrefGoogle Scholar
• 6c Yang WB. Yang YY. Gu YF. Wang SH. Chang CC. Lin CH. J. Org. Chem.  2002,  67:  3773 
  CrossrefGoogle Scholar
• 7 For a recent example, see: Waldscheck B. Streiff M. Notz W. Kinzy W. Schmidt RR. Angew. Chem. Int. Ed.  2001,  40:  4007 
  CrossrefGoogle Scholar
• 8 Johnson CR. Johns BA. Synlett  1997,  1406 
  Google Scholar
• 9 Griffin FK. Murphy PV. Paterson DE. Taylor RJK. Tetrahedron Lett.  1998,  39:  8179 
  CrossrefGoogle Scholar
• 10 Toth M. Somsak L. J. Chem. Soc., Perkin Trans. 1  2001,  942 
  CrossrefGoogle Scholar
• 11a Baudin JB. Hareau G. Julia SA. Ruel O. Tetrahedron Lett.  1991,  32:  1175 
  Google Scholar
• 11b Baudin JB. Hareau G. Julia SA. Lorne R. Ruel O. Bull. Soc. Chim. Fr.  1993,  130:  856 
  Google Scholar
• 12 For a recent review, see: Balkemore PR. J. Chem. Soc., Perkin Trans. 1  2002,  23:  2563 
  Google Scholar
• 13 For a recent example, see: Surprenant S. Chan WY. Berthelette C. Org. Lett.  2003,  5:  4851 ; and references cited therein
  CrossrefGoogle Scholar
• 14a Colombo MI. Zinczuk J. Mischne MP. Ruveda EA. Tetrahedron: Asymmetry  2001,  12:  1251 
  CrossrefGoogle Scholar
• 14b Colombo MI. Zinczuk J. Bohn ML. Ruveda EA. Tetrahedron: Asymmetry  2003,  14:  717 
  CrossrefGoogle Scholar
• 15 Csuk R. Glaenzer BI. Tetrahedron  1991,  47:  1655 
  Google Scholar

All compounds were characterised by NMR spectroscopy and HRMS. Data were identical to those reported in the literature.
Data for compound 5: ¹H NMR (300 MHz, CDCl₃): δ = 4.39 (d, 1 H, J = 4.3 Hz, H-2), 4.23 (s, 1 H, H-1′a), 4.05 (m, 2 H, H-3 and H-4), 3.95 (s, 1 H, H-1′b), 3.71 (dd, 1 H, J = 3.2 Hz, J = 11.5 Hz, H-5a), 3.63 (dd, 1 H, J = 3.4 Hz, H-5b), 0.90 (m, 27 H, CH₃), 0.59 (m, 18 H, CH₂). ¹³C NMR (75 MHz, CDCl₃): δ = 4.7, 5.2, 5.5, 7.1, 7.2, 7.3, 62.4, 72.7, 73.0, 82.6, 85.9, 163.4. IR: 1678 cm^-1 (C=C). [α]_D +15 (c 1, CHCl₃). HRMS (CI-MS): m/z calcd for C₂₄H₅₂O₄Si₃ [M + H]⁺: 489.3252; found: 489.3257