Download PDF
Synlett 2010(18): 2765-2770  
DOI: 10.1055/s-0030-1259000
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Nitroaldol Reaction of α-Keto Esters Catalyzed by a Copper(II)-Bisoxazolidine Complex

Hanhui Xu, Christian Wolf*
Department of Chemistry, Georgetown University, Washington, DC 20057, USA
Fax: +1(202)6876209; e-Mail: cw27@georgetown.edu;
Further Information

Publication History

Received 23 August 2010
Publication Date:
12 October 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A wide range of aliphatic and aromatic α-keto esters has been transformed to α-hydroxy-β-nitro esters via the Cu(II)-bisoxa­zolidine-catalyzed Henry reaction. In the presence of 10 mol% of the chiral catalyst, nitroaldol products were obtained in up to 95% yield and 76% ee.

Key words

asymmetric catalysis - nitroaldol reaction - chiral alcohols - copper - oxazolidine

    References and Notes

  • For reviews on the asymmetric Henry reaction, see:
  • 1a Boruwa J. Gogoi N. Saikia PP. Barua NC. Tetrahedron: Asymmetry  2006,  17:  3315 
    Google Scholar
  • 1b Palomo C. Oiarbide M. Laso A. Eur. J. Org. Chem.  2007,  2561 
    Google Scholar
  • 2a Kogami Y. Nakajima T. Ashizawa T. Kezuka S. Ikeno T. Yamada T. Chem. Lett.  2004,  614 
    Google Scholar
  • 2b Kogami Y. Nakajima T. Ikeno T. Yamada T. Synthesis  2004,  1947 
    Google Scholar
  • 3 Choudary BM. Ranganath KVS. Pal U. Kantam ML. Sreedhar B. J. Am. Chem. Soc.  2005,  127:  13167 
    CrossrefPubMedGoogle Scholar
  • 4a Trost BM. Yeh VSC. Angew. Chem. Int. Ed.  2002,  41:  861 
    Google Scholar
  • 4b Palomo C. Oiarbide M. Laso A. Angew. Chem. Int. Ed.  2005,  44:  3881 
    Google Scholar
  • 4c Colak M. Aral T. Hogoren H. Demirel N. Tetrahedron: Asymmetry  2007,  18:  1129 
    Google Scholar
  • 4d Kim HY. Oh K. Org. Lett.  2009,  11:  5682 
    Google Scholar
  • 5 Kowalczyk R. Kwiatkowski P. Skarzewski J. Jurczak J. J. Org. Chem.  2009,  74:  753 
    CrossrefGoogle Scholar
  • 6a Arai T. Watanabe M. Fujiwara A. Yokoyama N. Yanagisawa A. Angew. Chem. Int. Ed.  2006,  45:  5978 
    Google Scholar
  • 6b Xiong Y. Wang F. Huang X. Wen Y. Feng X. Chem. Eur. J.  2007,  13:  829 
    Google Scholar
  • 6c Jiang J.-J. Shi M. Tetrahedron: Asymmetry  2007,  18:  1376 
    Google Scholar
  • 6d Arai T. Takashita R. Endo Y. Watanabe M. Yanagisawa A. J. Org. Chem.  2008,  73:  4903 
    Google Scholar
  • 7a Christensen C. Juhl K. Hazell RG. Jørgensen KA. J. Org. Chem.  2002,  67:  4875 
    Google Scholar
  • 7b Evans DA. Seidel D. Rueping M. Lam HW. Shaw JT. Downey CW. J. Am. Chem. Soc.  2003,  125:  12692 
    Google Scholar
  • 7c Foltz C. Stecker B. Marconi G. Bellemin-Laponnaz S. Wadepohl H. Gade LH. Chem. Commun.  2005,  5115 
    Google Scholar
  • 7d Maheswaran H. Prasant KL. Krishna GG. Ravikumar B. Sridhar B. Kantam ML. Chem. Commun.  2006,  4066 
    Google Scholar
  • 7e Bandini M. Piccinelli F. Tommasi S. Umani-Ronchi A. Ventrici C. Chem. Commun.  2007,  616 
    Google Scholar
  • 7f Blay G. Climent E. Fernandez I. Hernandez-Olmos V. Pedro JR. Tetrahedron: Asymmetry  2006,  17:  2046 
    Google Scholar
  • 7g Ma K. You J. Chem. Eur. J.  2007,  13:  1863 
    Google Scholar
  • 7h Bandini M. Benaglia M. Sinisi R. Tommasi S. Umani-Ronchi A. Org. Lett.  2007,  9:  2151 
    Google Scholar
  • 7i Ginotra SK. Singh VK. Org. Biomol. Chem.  2007,  5:  3932 
    Google Scholar
  • 7j Arai T. Watanabe M. Yanagisawa A. Org. Lett.  2007,  9:  3595 
    Google Scholar
  • 7k Gan C. Can. J. Chem.  2008,  86:  261 
    Google Scholar
  • 7l Blay G. Domingo LR. Hernandez-Olmos V. Pedro JR. Chem. Eur. J.  2008,  4725 
    Google Scholar
  • 7m Tanaka K. Hachiken S. Tetrahedron Lett.  2008,  49:  2533 
    Google Scholar
  • 7n Selvakumar S. Sivasankaran D. Singh VK. Org. Biomol. Chem.  2009,  7:  3156 
    Google Scholar
  • 7o Zielinska-Blajet M. Skarzewski J. Tetrahedron: Asymmetry  2009,  20:  1992 
    Google Scholar
  • 8a Sasai J. Suzuki T. Arai S. Arai T. Shibasaki M.
    J. Am. Chem. Soc.  1992,  114:  4418 
    Google Scholar
  • 8b Sasai J. Suzuki T. Itoh N. Shibasaki M. Tetrahedron Lett.  1993,  34:  851 
    Google Scholar
  • 8c Sasai H. Zuzuki N. Itoh K. Tanaka T. Date K. Okamura K. Shibasaki M. J. Am. Chem. Soc.  1993,  115:  10372 
    Google Scholar
  • 8d Sohtome Y. Kato Y. Handa S. Aoyama N. Nagawa K. Matsunaga S. Shibasaki M. Org. Lett.  2008,  10:  2231 
    Google Scholar
  • 8e Nitabaru T. Kumagai N. Shibasaki M. Tetrahedron Lett.  2008,  49:  272 
    Google Scholar
  • 9a Trost BM. Yeh VSC. Ito H. Bremeyer N. Org. Lett.  2002,  4:  2621 
    Google Scholar
  • 9b Palomo C. Oiarbide M. Mielgo A. Angew. Chem. Int. Ed.  2004,  43:  5442 
    Google Scholar
  • 9c Gan C. Lai G. Zhang Z. Wang Z. Zhou M.-M. Tetrahedron: Asymmetry  2006,  17:  725 
    Google Scholar
  • 9d Sedlak M. Drabina P. Keder R. Hanusek J. Cisarova I. Ruzicka A.
    J. Organomet. Chem.  2006,  691:  2623 
    Google Scholar
  • 9e Bandini M. Piccinelli F. Tommasi S. Umani-Ronchi A. Ventrici C. Chem. Commun.  2007,  616 
    Google Scholar
  • 9f Mansawat W. Saengswang I. U-prasitwong P. Bhanthumnavin W. Vilaivan T. Tetrahedron Lett.  2007,  48:  4235 
    Google Scholar
  • 9g Colak M. Demirel N. Tetrahedron: Asymmetry  2008,  19:  635 
    Google Scholar
  • 9h Arai T. Yokoyama N. Yanagisawa A. Chem. Eur. J.  2008,  2052 
    Google Scholar
  • 10a Christensen C. Juhl K. Jørgensen KA. Chem. Commun.  2001,  2222 
    Google Scholar
  • 10b Du D.-M. Lu S.-F. Fang T. Xu J. J. Org. Chem.  2005,  70:  3712 
    Google Scholar
  • 10c Li H. Wang B. Deng L. J. Am. Chem. Soc.  2006,  128:  732 
    Google Scholar
  • 10d Pandya SU. Dickins RS. Parker D. Org. Biomol. Chem.  2007,  5:  3842 
    Google Scholar
  • 10e Qin B. Xiao X. Liu X. Huang J. Wen Y. Feng X. J. Org. Chem.  2007,  72:  9323 
    Google Scholar
  • 10f Blay G. Hernandez-Olmos V. Pedro JR. Org. Biomol. Chem.  2008,  6:  468 
    Google Scholar
  • 10g Takada K. Takemura N. Cho K. Sohtome Y. Nagasawa K. Tetrahedron Lett.  2008,  49:  1623 
    Google Scholar
  • 10h Bulut A. Aslant A. Dogan O. J. Org. Chem.  2008,  73:  7373 
    Google Scholar
  • 11a Tur F. Saa JM. Org. Lett.  2007,  9:  5079 
    Google Scholar
  • 11b Saa JM. Tur F. Gonzalez J. Chirality  2009,  21:  836 
    Google Scholar
  • 11c Bandini M. Sinisi R. Umani-Ronchi A. Chem. Commun.  2008,  4360 
    Google Scholar
  • 12 inventors; (catalogue no. 07-0488)  US 20070265255A1 patent pending. This ligand is commercially available at Strem
  • 13a Liu S. Wolf C. Org. Lett.  2008,  10:  1831 
    Google Scholar
  • 13b Yearick Spangler K. Wolf C. Org. Lett.  2009,  11:  4724 
    Google Scholar
  • For other bisoxazolidine-catalyzed enantioselective reactions, see:
  • 13c Wolf C. Liu S. J. Am. Chem. Soc.  2006,  128:  10996 
    Google Scholar
  • 13d Liu S. Wolf C. Org. Lett.  2007,  9:  2965 
    Google Scholar
14

A control experiment showed that the nitroaldol reaction proceeds very slowly in the presence of AgClO4 and only 12% of racemic 2 were obtained after 24 h. We therefore believe that the in situ formation of Cu(ClO4)2 from AgClO4 and CuCl2, which is visible by the precipitation of AgCl, is quantitative.