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Synthesis 2008(17): 2835-2839  
DOI: 10.1055/s-2008-1067224
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© Georg Thieme Verlag Stuttgart ˙ New York

Direct Synthesis of Protected Enantiopure 5-Cyano-3,4-dihydroxypyrrolidin-2-ones from β-Lactam Aldehydes Catalyzed by Iodine

Benito Alcaide*a, Pedro Almendros*b, Gema Cabreroa, M. Pilar Ruiza
a Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense, 28040 Madrid, Spain
Fax: +34(91)3944103; e-Mail: alcaideb@quim.ucm.es;
b Instituto de Química Orgánica General, CSIC, Juan de la Cierva 3, 28006 Madrid, Spain
Fax: +34(91)5644853; e-Mail: Palmendros@iqog.csic.es;
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Publication History

Received 11 June 2008
Publication Date:
11 August 2008 (online)

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Abstract

A single-step catalytic ring-expansion approach from 4-oxoazetidine-2-carbaldehydes to protected enantiopure 5-cyano-3,4-dihydroxypyrrolidin-2-ones has been achieved by the use of the commercially available and inexpensive reagent, molecular iodine, in the presence of tert-butyldimethyl cyanide. Interestingly, the catalyst directs the reaction toward the selective rearrangement reaction of the β-lactam nucleus rather than cyanohydrin formation.

Key words

catalysis - iodine - β-lactams - pyrrolidines - ring expansion

    References

  • 1a Compain P. Martin OR. Iminosugars: From Synthesis to Therapeutic Applications   Wiley; Chichester: 2007. 
  • 1b Curtis KL. Evinson EL. Handa S. Singh K. Org. Biomol. Chem.  2007,  5:  3544 
    Search in Google Scholar
  • 1c Asano N. Glycobiology  2003,  13:  93R 
    Search in Google Scholar
  • 1d Nishimura Y. Curr. Top. Med. Chem.  2003,  3:  575 
    Search in Google Scholar
  • 1e Asano N. Nash RJ. Molyneux RJ. Fleet GWJ. Tetrahedron: Asymmetry  2000,  11:  1645 
    Search in Google Scholar
  • 1f Legler G. In Iminosugars as Glycosidase Inhibitors: Nojirimycin and Beyond   Stütz AE. Wiley-VCH; Weinheim: 1999. 
  • 2 For a seminal review, see: Nájera C. Yus M. Tetrahedron: Asymmetry  1999,  10:  2245 
    CrossrefSearch in Google Scholar
  • For antibiotic use, see:
  • 3a Southgate R. Branch C. Coulton S. Hunt E. In Recent Progress in the Chemical Synthesis of Antibiotics and Related Microbial Products   Vol. 2:  Lukacs G. Springer; Berlin: 1993.  p.621 
    Search in Google Scholar
  • 3b Chemistry and Biology of β-Lactam Antibiotics   Vol. 1-3:  Morin RB. Gorman M. Academic; New York: 1982. 
  • For enzyme inhibition use, see:
  • 3c Veinberg G. Vorona M. Shestakova I. Kanepe I. Lukevics E. Curr. Med. Chem.  2003,  10:  1741 
    Search in Google Scholar
  • 3d Clader JW. J. Med. Chem.  2004,  47:  1 
    Search in Google Scholar
  • 3e Kvaerno L. Ritter T. Werder M. Hauser H. Carreira EM. Angew. Chem. Int. Ed.  2004,  43:  4653 
    Search in Google Scholar
  • For gene activation use, see:
  • 3f Rothstein JD. Patel S. Regan MR. Haenggeli C. Huang YH. Bergles DE. Jin L. Hoberg MD. Vidensky S. Chung DS. Toan SV. Bruijn LI. Su Z.-z. Gupta P. Fisher PB. Nature  2005,  433:  73 
    Search in Google Scholar
  • For selected reviews, see:
  • 4a Alcaide B. Almendros P. Aragoncillo C. Chem. Rev.  2007,  107:  4437 
    Search in Google Scholar
  • 4b Alcaide B. Almendros P. Curr. Med. Chem.  2004,  11:  1921 
    Search in Google Scholar
  • 4c Deshmukh ARAS. Bhawal BM. Krishnaswamy D. Govande VV. Shinkre BA. Jayanthi A. Curr. Med. Chem.  2004,  11:  1889 
    Search in Google Scholar
  • 4d Alcaide B. Almendros P. Synlett  2002,  381 
  • 4e Palomo C. Aizpurua JM. Ganboa I. Oiarbide M. Synlett  2001,  1813 
  • 5a Alcaide B. Almendros P. Cabrero G. Ruiz MP. Chem. Commun.  2008,  615 
  • For a review on β-lactam aldehydes, see:
  • 5b Alcaide B. Almendros P. Chem. Soc. Rev.  2001,  30:  226 
    Search in Google Scholar
  • 6 For a recent review, see: Togo H. Iida S. Synlett  2006,  2159 
    Thieme Connect
  • 7a Yadav JS. Reddy BVS. Reddy MS. Prasad AR. Tetrahedron Lett.  2002,  43:  9703 
    Search in Google Scholar
  • 7b Royer L. De S K. Gibbs RA. Tetrahedron Lett.  2005,  46:  4595 
    Search in Google Scholar
  • 8 Alcaide B. Almendros P. Cabrero G. Ruiz MP. J. Org. Chem.  2007,  72:  7980 
    CrossrefPubMedSearch in Google Scholar