Synthesis 2005(6): 957-960  
DOI: 10.1055/s-2005-861796
PAPER
© Georg Thieme Verlag Stuttgart · New York

Catalytic Highly Enantioselective Direct Amination of 1,3-Diketones

Mauro Marigo, Nagaswamy Kumaragurubaran, Karl Anker Jørgensen*
Danish National Research Foundation: Center for Catalysis, Department of Chemistry, Aarhus University, 8000 Aarhus C, Denmark
e-Mail: [email protected];
Further Information

Publication History

Received 4 November 2004
Publication Date:
21 February 2005 (online)

Abstract

The direct asymmetric amination of 1,3-diketones by azodicarboxylates catalyzed by chiral copper(II) bisoxazolines is presented. Screening of chiral bisoxazoline ligands, Lewis acids, solvents, and other reaction parameters led to an enantioselective direct amination in the 2-position of 1,3-diketones and the optically active functionalized molecules were obtained in high yields and enantioselectivities.

    References

  • For some recent reviews see:
  • 1a Modern Amination Methods   Ricci A. Wiley-VCH; Weinheim: 2000. 
  • 1b Erdik E. Tetrahedron  2004,  60:  8647 
  • 1c Greck C. Drouillat B. Thomassigny C. Eur. J. Org. Chem.  2004,  1377 
  • 2a For a recent highlight see: Duthaler RO. Angew. Chem. Int. Ed.  2003,  42:  975 
  • 2b See also: Ma J.-A. Angew. Chem. Int. Ed.  2003,  42:  4290 
  • 3a Juhl K. Jørgensen KA. J. Am. Chem. Soc.  2002,  124:  2420 
  • 3b Marigo M. Juhl K. Jørgensen KA. Angew. Chem. Int. Ed.  2003,  42:  1367 
  • 3c Evans DA. Nelson SG. J. Am. Chem. Soc.  1997,  119:  6542 
  • 3d Evans DA. Nelson SG. Org. Lett.  1999,  1:  595 
  • 3e See also: Yamamoto Y. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  4128 
  • 3f Moniyama N. Yamamoto H. J. Am. Chem. Soc.  2004,  126:  5360 
  • 4a Bøgevig A. Juhl K. Kumaragurubaran N. Zhuang W. Jørgensen KA. Angew. Chem. Int. Ed.  2002,  41:  1790 
  • 4b List B. J. Am. Chem. Soc.  2002,  124:  5656 
  • 4c Kumaragurubaran N. Juhl K. Zhuang W. Bøgevig A. Jørgensen KA. J. Am. Chem. Soc.  2002,  124:  6254 
  • 4d Vogt H. Vanderheiden S. Bräse S. Chem. Commun.  2003,  2448 
  • 5 Hamashima Y. Hotta D. Sodeoka M. J. Am. Chem. Soc.  2002,  124:  11240 
  • For metal-catalyzed direct amination reactions leading to racemic products see:
  • 6a Fioravanti S. Morreale A. Pellacani L. Tardella PA. Tetrahedron Lett.  2001,  42:  1171 
  • 6b Clarine J. Gálvez N. Marchi C. Moreno-Manas M. Vallribera A. Molins E. Tetrahedron  1999,  55:  7331 
  • 7 One example of catalytic enantioselective amination of a 1,3-diketone with good enantioselectivity using a chinchona alkaloid as the catalyst is known: Saaby S. Bella M. Jørgensen KA. J. Am. Chem. Soc.  2004,  126:  8120 
  • For reviews of C2-symmetric bisoxazoline-Lewis acid complexes as catalyst see:
  • 8a Ghosh AK. Mathivanen P. Cappiello J. Tetrahedron: Asymmetry  1998,  9:  1 
  • 8b Jørgensen KA. Johannsen M. Yao S. Audrian H. Thorhauge J. Acc. Chem. Res.  1999,  32:  605 
  • 8c Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 
  • 8d Basek R. Synlett  2003,  1223 
  • 9 See: Thorhauge J. Roberson M. Hazell RG. Jørgensen KA. Chem.-Eur. J.  2002,  8:  1888 ; and references therein