Download PDF
Synlett 2005(17): 2670-2672  
DOI: 10.1055/s-2005-917101
LETTER
© Georg Thieme Verlag Stuttgart · New York

Design and Synthesis of a Chiral N-Tethered Bis(imidazoline) Ligand

Takayoshi Arai*a, Tomoe Mizukamia, Naota Yokoyamab, Daisuke Nakazatob, Akira Yanagisawaa
a Department of Chemistry, Faculty of Science, Chiba University, Inage 263-8522, Japan
Fax: +81(43)2902889; e-Mail: tarai@faculty.chiba-u.jp;
b Graduate School of Science and Technology, Chiba University, Inage 263-8522, Japan
Further Information

Publication History

Received 1 August 2005
Publication Date:
05 October 2005 (online)

    Permissions and Reprints All articles of this category

Abstract

A chiral nitrogen-tethered bis (imidazoline) ligand (Nb-imidazoline) was newly designed and synthesized in a divergent strategy. Thus, a single coupling reaction of primary amine with two molecules of chloromethylated imidazoline provided the Nb-imidazoline. The copper(II) triflate complex of Nb-imidazoline catalyzed a trans-selective cyclopropanation of styrene with ethyl di­azoacetate to give the adduct in high chemical yield with good enantiomeric excess up to 83%.

Key word

asymmetric catalysis - ligands - imidazoline - copper - ­cyclopropanation

    References

  • 1a Asymmetric Catalysis in Organic Synthesis   Noyori R. Wiley; New York: 1994. 
    Google Scholar
  • 1b Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer; Berlin: 1999. 
    Google Scholar
  • 1c Transition Metals for Organic Synthesis   2nd ed.:  Beller M. Bolm C. Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 2a Ghosh AK. Mathivanan P. Cappiello J. Tetrahedron: Asymmetry  1998,  9:  1 
    CrossrefGoogle Scholar
  • 2b Jørgensen KA. Johannsen M. Yao S. Audrain H. Thorhauge J. Acc. Chem. Res.  1999,  32:  605 
    CrossrefGoogle Scholar
  • Recent progress on chiral ligands containing imidazoline motif:
  • 3a Morimoto T. Tachibana K. Achiwa K. Synlett  1997,  783 
    CrossrefGoogle Scholar
  • 3b Davenport AJ. Davies DL. Fawcett J. Russell DR. J. Chem. Soc., Perkin Trans. 1  2001,  1500 
    CrossrefGoogle Scholar
  • 3c Menges F. Neuburger M. Pfaltz A. Org. Lett.  2002,  4:  4713 
    CrossrefGoogle Scholar
  • 3d Busacca CA. Grossbach D. So RC. O’Brien EM. Spinelli EM. Org. Lett.  2003,  5:  595 
    CrossrefGoogle Scholar
  • 3e Casey M. Smyth MP. Synlett  2003,  102 
    CrossrefGoogle Scholar
  • 3f Guiu E. Claver C. Benet-Buchholz J. Castillón S. Tetrahedron: Asymmetry  2004,  15:  3365 
    CrossrefGoogle Scholar
  • 3g Bastero A. Claver C. Ruiz A. Castillón S. Daura E. Bo C. Zangrando E. Chem. Eur. J.  2004,  10:  3747 
    CrossrefGoogle Scholar
  • 4 Zhang et al. reported the N-tethered bis(oxazoline) as ambox: Jiang Y. Jiang Q. Zhang X. J. Am. Chem. Soc.  1998,  120:  3817 
    CrossrefGoogle Scholar
  • 5 Mylari BL. Scott PJ. Zembrowski WJ. Synth. Commun.  1989,  19:  2921 
    Google Scholar
  • Recent progress in Cu-bis(oxazoline)-catalyzed asymmetric benzoylation of 1,2-diol:
  • 7a Matsumura Y. Maki T. Murakami S. Onomura O. J. Am. Chem. Soc.  2003,  125:  2052 
    CrossrefGoogle Scholar
  • 7b Matsumura Y. Maki T. Tsurumaki K. Onomura O. Tetrahedron Lett.  2004,  45:  9131 
    CrossrefGoogle Scholar
  • 7c Gissibl A. Finn MG. Reiser O. Org. Lett.  2005,  7:  2325 
    CrossrefGoogle Scholar
  • 8 During the preparation of this manuscript, Beller et al. reported a similar type of pyridinebisimidazoline ligand for a Ru-catalyzed asymmetric epoxidation: Bhor S. Anilkumar G. Tse MK. Klawonn M. Döbler C. Bitterlich B. Grotevendt A. Beller M. Org. Lett.  2005,  7:  3393 
    CrossrefPubMedGoogle Scholar
6

Nb-imidazoline is an abbreviation of N-tethered bis(imidazoline).