Download PDF
Synlett 2012(1): 57-61  
DOI: 10.1055/s-0031-1289875
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective Intramolecular Hydroamination of N-Alkenyl Ureas Catalyzed by tropos BIPHEP-Gold(I) Complexes with Au-Au Interaction

Masafumi Kojima, Koichi Mikami*
Department of Applied Chemistry, Tokyo Institute of Technology, Tokyo 152-8550, Japan
Fax: +81(3)57342776; e-Mail: mikami.k.ab@m.titech.ac.jp;
Further Information

Publication History

Received 2 October 2011
Publication Date:
11 November 2011 (online)

    Permissions and Reprints All articles of this category

Corrected by:

Enantioselective Intramolecular Hydroamination of N-Alkenyl Ureas Catalyzed by tropos BIPHEP-Gold(I) Complexes with Au-Au InteractionSynlett 2012; 2012(01): e1-e1
DOI: 10.1055/s-0031-1290122

Abstract

Dinuclear gold complexes significantly accelerate intramolecular hydroamination of N-alkenyl ureas via proximal and bimetallic activation of alkene and urea. Tropos BIPHEP-gold complexes having Au-Au interaction affords higher enantioselectivity than the BINAP-gold counterparts without Au-Au interaction.

Key words

gold - asymmetric catalysis - hydroamination - alkenes - bimetallic activation

    References

  • For reviews on enantioselective gold catalysis, see:
  • 1a Bongers N. Krause N. Angew. Chem. Int. Ed.  2008,  47:  2178 
    Search in Google Scholar
  • 1b Widenhoefer RA. Chem. Eur. J.  2008,  14:  5382 
    Search in Google Scholar
  • 1c Sengupta S. Shi X. ChemCatChem  2010,  2:  609 
    Search in Google Scholar
  • 1d Pradal A. Toullec PY. Michelet V. Synthesis  2011,  1501 
  • For reviews on gold catalysis, see:
  • 2a Li Z. Brouwer C. He C. Chem. Rev.  2008,  108:  3239 
    Search in Google Scholar
  • 2b Arcadi A. Chem. Rev.  2008,  108:  3266 
    Search in Google Scholar
  • 2c Gorin DJ. Sherry BD. Toste FD. Chem. Rev.  2008,  108:  3351 
    Search in Google Scholar
  • 2d Shen HC. Tetrahedron  2008,  64:  3885 
    Search in Google Scholar
  • 2e Hashmi ASK. Angew. Chem. Int. Ed.  2010,  49:  5232 
    Search in Google Scholar
  • 2f Corma A. Leyva-Pérez A. Sabater MJ. Chem. Rev.  2011,  111:  1657 
    Search in Google Scholar
  • 2g Krause N. Winter C. Chem. Rev.  2011,  111:  1994 
    Search in Google Scholar
  • 3a Han X. Widenhoefer RA. Angew. Chem. Int. Ed.  2006,  45:  1747 
    Search in Google Scholar
  • 3b Bender CF. Widenhoefer RA. Chem. Commun.  2006,  4143 
  • 3c Zhang J. Yang C.-G. He C. J. Am. Chem. Soc.  2006,  128:  1798 
    Search in Google Scholar
  • 3d Bender CF. Widenhoefer RA. Org. Lett.  2006,  8:  5303 
    Search in Google Scholar
  • 4 Enantioselective intermolecular hydroamination of unactivated alkenes, see: Zhang Z. Lee SD. Widenhoefer RA. J. Am. Chem. Soc.  2009,  131:  5372 
    Search in Google Scholar
  • X-ray analysis of BIPHEP-gold complexes:
  • 5a Aikawa K. Kojima M. Mikami K. Adv. Synth. Catal.  2010,  352:  3131 
    Search in Google Scholar
  • X-ray analysis of BINAP-gold complexes:
  • 5b Tarselli MA. Chianese AR. Lee SJ. Gagné MR. Angew. Chem. Int. Ed.  2007,  46:  6670 
    Search in Google Scholar
  • 6 Enantioselective gold-catalyzed reaction via bimetallic activation, see: Bandini M. Eichholzer A. Angew. Chem. Int. Ed.  2009,  48:  9533 
    Search in Google Scholar
  • The dinuclear gold complexes having Au-Au interaction were recently reported to provide higher enantioselectivity than the dinuclear gold complexes without Au-Au interaction, see:
  • 7a Liu F. Qian D. Li L. Zhao X. Zhang J. Angew. Chem. Int. Ed.  2010,  49:  6669 
    Search in Google Scholar
  • 7b Wang M.-Z. Zhou C.-Y. Guo Z. Wong EL.-M. Wong M.-K. Che C.-M. Chem. Asian. J.  2011,  6:  812 
    Search in Google Scholar
  • 8 For a review, see: Mikami K. Aikawa K. Yusa Y. Jodry JJ. Yamanaka M. Synlett  2002,  1561 
  • Metal salts of chiral phosphate anions have been used as effective enantioselective catalysts, see:
  • 9a Inanaga J. Sugimoto Y. Hanamoto T. New J. Chem.  1995,  19:  707 
    Search in Google Scholar
  • 9b Inanaga J. Furuno H. Hayano T. Chem. Rev.  2002,  102:  2211 
    Search in Google Scholar
  • 9c Hamilton GL. Kang EJ. Mba M. Toste FD. Science  2007,  317:  496 
    Search in Google Scholar
  • 9d Lacour J. Molareda D. Chem. Commun.  2009,  7073 
  • 10 Aikawa K. Kojima M. Mikami K. Angew. Chem. Int. Ed.  2009,  48:  6073 
    Search in Google Scholar
  • 11Quite recently Toste and co-workers clearly disclosed that the generation of an acidic species was important for the catalytic turnover in the hydroamination of unactivated alkenes via protodeauration:
  • 11 LaLonde RL. Brenzovich WE. Benitez D. Tkatchouk E. Kelley K. Goddard WA. Toste FD. Chem. Sci.  2010,  1:  226 
    Search in Google Scholar