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Synlett 2009(14): 2261-2264  
DOI: 10.1055/s-0029-1217808
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Hybrid Diamines Derived from 1,1′-Binaphthyl-2,2′-diamine and α-Amino Acids as Organocatalysts for 1,3-Dipolar Cycloaddition of Aromatic Nitrones to (E)-Crotonaldehyde

Łukasz Weselińskia, Paweł Stępniaka, Janusz Jurczak*a,b
a Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
b Institute of Organic Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
Fax: +48(22)6326681; e-Mail: jurczak@icho.edu.pl;
Further Information

Publication History

Received 4 May 2009
Publication Date:
07 August 2009 (online)

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Abstract

Homochiral derivatives of 1,1′-binaphthyl-2,2′-diamine and various α-amino acids were prepared using a convenient procedure. They were tested as organocatalysts for 1,3-dipolar cyclo­addition of aromatic nitrones to (E)-crotonaldehyde. The l-phenylalanine-based catalyst 10 afforded superior results, with good endo diastereoselectivity, and enantioselectivity of up to 95% ee.

Key words

α-amino acids - asymmetric organocatalysis - binaph­thyl derivatives - 1,3-dipolar cycloaddition - nitrones

    References and Notes

  • 1 Kowalczyk B. Tarnowska A. Weseliński Ł. Jurczak J. Synlett  2005,  2373 
    Article in Thieme ConnectGoogle Scholar
  • 2a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
    Google Scholar
  • 2b Berkessel A. Gröger H. Asymmetric Organocatalysis   Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 2c Erkkilä A. Majander I. Pihko PM. Chem. Rev.  2007,  107:  5416 
    Google Scholar
  • 2d Mukherjee S. Yang JW. Hoffmann S. List B. Chem. Rev.  2007,  107:  5471 
    Google Scholar
  • 2e Dalko PI. Enantioselective Organocatalysis   Wiley-VCH; Weinheim: 2007. 
    Google Scholar
  • 2f Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2007,  18:  2249 
    Google Scholar
  • 2g Pellissier H. Tetrahedron  2007,  63:  9267 
    Google Scholar
  • 2h Peng F. Shao Z. J. Mol. Catal. A: Chem.  2008,  285:  1 
    Google Scholar
  • 2i Bartoli G. Melchiorre P. Synlett  2008,  1759 
    Google Scholar
  • 2j Dondoni A. Massi A. Angew. Chem. Int. Ed.  2008,  47:  4638 
    Google Scholar
  • 2k Melchiorre P. Marigo M. Carlone A. Bartoli G. Angew. Chem. Int. Ed.  2008,  47:  6138 
    Google Scholar
  • 3 Gryko D. Kowalczyk B. Zawadzki Ł. Synlett  2006,  1059 
    Article in Thieme ConnectGoogle Scholar
  • 4a Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2006,  17:  729 
    Google Scholar
  • 4b Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2006,  17:  1027 
    Google Scholar
  • 4c Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2006,  17:  1493 
    Google Scholar
  • 4d Guizetti S. Benaglia M. Pignataro L. Puglisi A. Tetrahedron: Asymmetry  2006,  17:  2754 
    Google Scholar
  • 4e Guillena G. Hita MC. Nájera C. ARKIVOC  2007,  (iv):  260 
    Google Scholar
  • 4f Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2007,  18:  1272 
    Google Scholar
  • 4g Guillena G. Hita MC. Nájera C. Tetrahedron: Asymmetry  2007,  18:  2300 
    Google Scholar
  • 4h Ma G.-N. Zhang Y.-P. Shi M. Synthesis  2007,  197 
    Google Scholar
  • 4i Guillena G. Hita MC. Nájera C. Viózquez SF. J. Org. Chem.  2008,  73:  5933 
    Google Scholar
  • 5 Jen WS. Wiener JJM. MacMillan DWC. J. Am. Chem. Soc.  2000,  122:  9874 
    CrossrefGoogle Scholar
  • 6a Karlsson S. Högberg H.-E. Tetrahedron: Asymmetry  2002,  13:  923 
    Google Scholar
  • 6b Karlsson S. Högberg H.-E. Eur. J. Org. Chem.  2003,  2782 
    Google Scholar
  • 6c Chow SS. Nevalainen M. Evans CA. Johannes CW. Tetrahedron Lett.  2007,  48:  277 
    Google Scholar
  • 6d Lemay M. Trant J. Ogilvie WW. Tetrahedron  2007,  63:  11644 
    Google Scholar
  • 7 Puglisi A. Benaglia M. Cinquini M. Cozzi F. Celentano G. Eur. J. Org. Chem.  2004,  567 
    CrossrefGoogle Scholar
  • 8a Frederickson M. Tetrahedron  1997,  53:  403 
    Google Scholar
  • 8b Gothelf KV. Jørgensen KA. Chem. Rev.  1998,  98:  863 
    Google Scholar
  • 9 Compared to crotonaldehyde, acrolein was more difficult to optimize, as reported in: Jen WS. Ph. D. Thesis   California Institute of Technology; USA: 2004. 
    Google Scholar
  • 11 Hashimoto T. Omote M. Kano T. Maruoka K. Org. Lett.  2007,  9:  4805 
    CrossrefGoogle Scholar
10

The reaction was performed using 0 equiv, 3 equiv, 6 equiv and 12 equiv of H2O and no significant difference in yield and diastereoselectivity was observed in all cases, although the enantioselectivity in the absence of H2O was slightly lower; therefore 3 equiv of H2O were always added to the reaction mixture.

12

General Procedure for 1,3-Dipolar Cycloaddition: A solution of the nitrone (0.25 mmol) in nitromethane (1 mL) was placed in a vial, and H2O (3 equiv), the catalyst and the acid co-catalyst were added and the resulting mixture was cooled to 4 ˚C. Then the freshly distilled α,β-unsaturated aldehyde was added (4 equiv, followed by 3 equiv at 24 h intervals) and the mixture was left for a specific period of time. Then it was filtered through a silica gel plug with aid of CH2Cl2, and then concentrated. After purification by flash chromatography (hexane-EtOAc), the residual oils were reduced to the corresponding alcohols with NaBH4 in MeOH. The ee values of purified alcohols were determined by chiral HPLC using CHIRALCEL OD or OD-H columns (95-98% hexane-isopropanol, flow: 1 mL/min).

13

All new compounds obtained here had correct analytical and spectral data.