Download PDF
Synthesis 2009(9): 1557-1563  
DOI: 10.1055/s-0029-1216635
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselectivity Switch in Direct Asymmetric Aminoxylation Catalyzed by Binaphthyl-Based Chiral Secondary Amines

Taichi Kano, Akihiro Yamamoto, Fumitaka Shirozu, Keiji Maruoka*
Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo, Kyoto 606-8502, Japan
Fax: +81(757)534041; e-Mail: maruoka@kuchem.kyoto-u.ac.jp;
Further Information

Publication History

Received 16 January 2009
Publication Date:
14 April 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

Binaphthyl-based amino acids (S)-1 and an aminosulfonamide (S)-2 were applied for direct asymmetric aminoxylation with nitrosobenzene. In the presence of either (S)-1 or (S)-2, the aminoxylation of aldehydes proceeded smoothly, and subsequent reduction with NaBH4 gave 2-aminoxyl alcohols with good to excellent enantioselectivities. In each case, binaphthyl-based chiral amine catalysts (S)-1 and (S)-2, which have the identical axial chirality, gave opposite enantiomers as the major product. This method represents a rare example of the direct asymmetric aminoxylation by a non-proline type catalyst.

Key words

enamine catalysis - asymmetric aminoxylation - organocatalyst

    References

  • For reviews, see:
  • 1a Adam W. Krebs O. Chem. Rev.  2003,  103:  4131 
    Google Scholar
  • 1b Merino P. Tejero T. Angew. Chem. Int. Ed.  2004,  43:  2995 
    Google Scholar
  • 1c Janey JM. Angew. Chem. Int. Ed.  2005,  44:  4292 
    Google Scholar
  • 1d Yamamoto H. Momiyama N. Chem. Commun.  2005,  3514 
    Google Scholar
  • 1e Yamamoto Y. Yamamoto H. Eur. J. Org. Chem.  2006,  2031 
    Google Scholar
  • 1f Yamamoto H. Kawasaki M. Bull. Chem. Soc. Jpn.  2007,  80:  595 
    Google Scholar
  • 2 Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2003,  125:  6038 
    CrossrefGoogle Scholar
  • Representative papers:
  • 3a Zhong G. Angew. Chem. Int. Ed.  2003,  42:  4247 
    Google Scholar
  • 3b Brown SP. Brochu MP. Sinz CJ. MacMillan DWC. J. Am. Chem. Soc.  2003,  125:  10808 
    Google Scholar
  • 3c Hayashi Y. Yamaguchi J. Hibino K. Shoji M. Tetrahedron Lett.  2003,  44:  8293 
    Google Scholar
  • 3d Bøgevig A. Sundén H. Córdova A. Angew. Chem. Int. Ed.  2004,  43:  1109 
    Google Scholar
  • 3e Hayashi Y. Yamaguchi J. Sumiya T. Shoji M. Angew. Chem. Int. Ed.  2004,  43:  1112 
    Google Scholar
  • 3f Yamamoto Y. Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  5962 
    Google Scholar
  • 3g Momiyama N. Torii H. Saito S. Yamamoto H. Proc. Natl. Acad. Sci. U.S.A.  2004,  101:  5374 
    Google Scholar
  • 3h Hayashi H. Yamaguchi J. Sumiya T. Hibino K. Shoji M. J. Org. Chem.  2004,  69:  5966 
    Google Scholar
  • 3i Wang W. Wang J. Li H. Liao L. Tetrahedron Lett.  2004,  45:  7235 
    Google Scholar
  • 3j Ramachary DB. Barbas CF. Org. Lett.  2005,  7:  1577 
    Google Scholar
  • 3k Huang K. Huang Z.-Z. Li X.-L. J. Org. Chem.  2006,  71:  8320 
    Google Scholar
  • 3l Font D. Bastero A. Sayalero S. Jimeno C. Pericàs MA. Org. Lett.  2007,  9:  1943 
    Google Scholar
  • Representative papers on the asymmetric synthesis of natural products and chiral building blocks via organocatalytic aminoxylation:
  • 4a Enders D. Lenzen A. Müller M. Synthesis  2004,  1486 
    Google Scholar
  • 4b Zhong G. Chem. Commun.  2004,  606 
    Google Scholar
  • 4c Zhong G. Yu Y. Org. Lett.  2004,  6:  1637 
    Google Scholar
  • 4d Kumarn S. Shaw DM. Longbottom DA. Ley SV. Org. Lett.  2005,  7:  4189 
    Google Scholar
  • 4e Kumarn S. Shaw DM. Longbottom DA. Ley SV. Chem. Commun.  2006,  3211 
    Google Scholar
  • 4f Kotkar SP. Sudalai A. Tetrahedron: Asymmetry  2006,  17:  1738 
    Google Scholar
  • 4g Kim S.-G. Park T.-H. Kim BJ. Tetrahedron Lett.  2006,  47:  6369 
    Google Scholar
  • 4h Kotkar SP. Sudalai A. Tetrahedron Lett.  2006,  47:  6813 
    Google Scholar
  • 4i Talluri SK. Sudalai A. Tetrahedron  2007,  63:  9758 
    Google Scholar
  • 5a Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2005,  127:  1080 
    Google Scholar
  • 5b Momiyama N. Yamamoto Y. Yamamoto H. J. Am. Chem. Soc.  2007,  129:  1190 
    Google Scholar
  • 6 Momiyama N. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  5360 
    CrossrefGoogle Scholar
  • 7a Guo H.-M. Cheng L. Cun L.-F. Gong L.-Z. Mi A.-Q. Jiang Y.-Z. Chem. Commun.  2006,  429 
    Google Scholar
  • 7b Kano T. Ueda M. Takai J. Maruoka K. J. Am. Chem. Soc.  2006,  128:  6046 
    Google Scholar
  • 7c Kim S.-G. Park T.-H. Tetrahedron Lett.  2006,  47:  9067 
    Google Scholar
  • 7d Palomo C. Vera S. Velilla I. Mielgo A. Gómez-Bengoa E. Angew. Chem. Int. Ed.  2007,  46:  8054 
    Google Scholar
  • 8 López-Cantarero CJ. Cid MB. Poulsen TB. Bella M. García Ruano JL. Jørgensen KA. J. Org. Chem.  2007,  72:  7062 
    CrossrefGoogle Scholar
  • 9a Yamamoto Y. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  4128 
    Google Scholar
  • 9b Yamamoto Y. Yamamoto H. Angew. Chem. Int. Ed.  2005,  44:  7082 
    Google Scholar
  • 9c Jana CK. Studer A. Angew. Chem. Int. Ed.  2007,  46:  6542 
    Google Scholar
  • 10a Kano T. Takai J. Tokuda O. Maruoka K. Angew. Chem. Int. Ed.  2005,  44:  3055 
    Google Scholar
  • 10b Kano T. Tokuda O. Takai J. Maruoka K. Chem. Asian J.  2006,  1:  210 
    Google Scholar
  • 11 Kano T. Yamaguchi Y. Maruoka K. Angew. Chem. Int. Ed.  2007,  46:  1738 
    CrossrefGoogle Scholar
  • 12a Kano T. Yamaguchi Y. Tokuda O. Maruoka K. J. Am. Chem. Soc.  2005,  127:  16408 
    Google Scholar
  • 12b Kano T. Yamaguchi Y. Maruoka K. Angew. Chem. Int. Ed.  2009,  48:  1838 
    Google Scholar
  • 13a Kano T. Yamamoto A. Mii H. Takai J. Shirakawa S. Maruoka K. Chem. Lett.  2008,  37:  250 
    Google Scholar
  • 13b Kano T. Yamamoto A. Maruoka K. Tetrahedron Lett.  2008,  49:  5369 
    Google Scholar
  • 14 Ooi T. Kameda M. Maruoka K. J. Am. Chem. Soc.  2003,  125:  5139 
    CrossrefPubMedGoogle Scholar
15

CCDC-710886 contains the supplementary crystallographic data of (S)-2˙HCl salt for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.