Synlett 2007(20): 3193-3197  
DOI: 10.1055/s-2007-992381
LETTER
© Georg Thieme Verlag Stuttgart · New York

Diastereoselective Conjugate Radical Additions to β-Pyranones

Mukund P. Sibi*, Arvin Yu
Department of Chemistry, North Dakota State University, Fargo, ND 58105, USA
Fax: [email protected];
Further Information

Publication History

Received 5 July 2007
Publication Date:
21 November 2007 (online)

Abstract

We have developed a convenient protocol for functionalization of β-pyranones. Conjugate radical addition and tandem addition-trapping protocols allow for accessing highly substituted pyrones in a single operation with high selectivity.

    References and Notes

  • 1a Radicals in Organic Synthesis   Vol. 1 and 2:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001. 
  • 1b Sibi MP. Manyem S. Zimmerman J. Chem. Rev.  2003,  103:  3263 
  • 1c Zimmerman J. Sibi MP. Top. Curr. Chem.  2006,  263:  107 
  • 2 For a recent review on tandem radical reactions, see: Albert M. Fensterbank L. Lacote E. Malacria M. Top. Curr. Chem.  2006,  264:  1 
  • 3 Sibi MP. Zimmerman J. J. Am. Chem. Soc.  2006,  128:  13346 
  • 4 van der Deen H. Kellogg RM. Feringa BL. Org. Lett.  2000,  2:  1593 
  • For work from Fraser-Reid and co-workers, see:
  • 5a Tsang R. Fraser-Reid B. J. Org. Chem.  1992,  57:  1065 
  • 5b Fraser-Reid B. Holder NL. Hicks DR. Walker DL. Can. J. Chem.  1977,  55:  3978 
  • 5c Benko Z. Fraser-Reid B. Mariano PS. Beckwith ALJ. J. Org. Chem.  1988,  53:  2066 
  • For selected examples on the use of β-pyranones in synthesis from other groups, see:
  • 5d Babu RS. Zhou M. O’Doherty GA. J. Am. Chem. Soc.  2004,  121:  3428 
  • 5e Guo H. O’Doherty GA. Org. Lett.  2005,  7:  3921 
  • 5f Shan M. O’Doherty GA. Org. Lett.  2006,  8:  5149 
  • 5g Comely AC. Eelkema R. Minnaard AJ. Feringa BL. J. Am. Chem. Soc.  2003,  125:  8714 
  • 5h van den Heuvel M. Cuiper AD. van der Deen H. Kellogg RM. Feringa BL. Tetrahedron Lett.  1997,  38:  1655 
  • 5i Fürstner A. Feyen F. Prinz H. Waldmann H. Angew. Chem. Int. Ed.  2003,  42:  5361 
  • 5j Krishnan KS. Smitha M. Suresh E. Radhakrishnan KV. Tetrahedron  2006,  62:  12345 
  • 5k Panfil I. Chmielewski M. Tetrahedron  1985,  41:  4713 
  • 5l Giese B. Witzel T. Tetrahedron Lett.  1987,  28:  2571 
  • 6 Compound 5 was prepared in racemic form using a literature procedure. See: Caddick S. Khan S. Frost LM. Cheung S. Pairaudeau G. Tetrahedron  2000,  56:  8953 
  • For recent reviews ,see:
  • 8a Baguley PA. Walton JC. Angew. Chem. Int. Ed.  1998,  37:  3072 
  • 8b Parsons AF. Chem. Br.  2002,  38:  42 
  • Alternatives to tin hydrides - selected examples:
  • 8c Chatgilialoglu C. Acc. Chem. Res.  1992,  25:  188 
  • 8d Leca D. Fensterbank L. Lacote E. Malacria M. Chem. Soc. Rev.  2005,  34:  858 
  • 8e Studer A. Amrein S. Synthesis  2002,  835 
  • 8f Graham SR. Murphy JA. Kennedy AR. J. Chem. Soc., Perkin Trans. 1  1999,  3071 
  • 8g Studer A. Amrein S. Schleth F. Schulte T. Walton JC. J. Am. Chem. Soc.  2003,  125:  5726 
  • 8h Cho DH. Jang DO. Bull. Korean Chem. Soc.  2003,  24:  15 
  • 8i Khan TA. Tripoli R. Crawford JJ. Martin CG. Murphy JA. Org. Lett.  2003,  5:  2971 
  • 9 For an example on the use of functionalized radicals in conjugate addition, see: Sibi MP. Guerrero M. Synthesis  2005,  1528 
  • For related examples of stereochemical control with 6-acyloxy-3-pyranones, see:
  • 10a Bashiardes G. Cano C. Mauze B. Synlett  2005,  587 
  • 10b Sugawara K. Imanishi Y. Hashiyama T. Heterocycles  2007,  71:  597 
  • For selected review articles, see:
  • 11a Sibi MP. Porter NA. Acc. Chem. Res.  1999,  32:  163 
  • 11b Ryu I. Sonoda N. Curran DP. Chem. Rev.  1996,  96:  177 
  • 11c Curran DP. Aldrichimica Acta  2000,  33:  104 
  • 11d Rosenstein IJ. In Radicals in Organic Synthesis   Vol. 1:  Renaud P. Sibi MP. Wiley-VCH; New York: 2001.  p.50-71  
  • For intermolecular radical addition and allyl stannane trapping, see:
  • 11e Sibi MP. Chen J. J. Am. Chem. Soc.  2001,  123:  9472 
  • 11f Sibi MP. Aasmul M. Hasegawa H. Subramanian T. Org. Lett.  2003,  5:  2883 
  • 11g Sibi MP. Ji J. J. Org. Chem.  1996,  61:  6090 
  • 11h Ueda M. Miyabe H. Sugino H. Miyata O. Naito T. Angew. Chem. Int. Ed.  2005,  44:  6190 
  • Compounds 8 and 11 were prepared following literature procedures. Commercially available enantiopure (R)- and (S)-2-furyl ethanols were converted into 8 and 11, respectively. See:
  • 12a

    Ref. 5a.

  • 12b Zhou M. O’Doherty GA. Org. Lett.  2006,  8:  4339 
  • 12c Zhou M. O’Doherty GA. J. Org. Chem.  2007,  72:  2485 
  • 12d Yonghong G. Fangning Z. Xinfu P. J. Chem. Res., Synop.  1999,  488 
7

All new compounds showed analytical and spectral characteristics consistent with their structure. An experimental procedure and spectral data for select products are provided.