PDF herunterladen
Synlett 2012(5): 699-705  
DOI: 10.1055/s-0031-1290132
ACCOUNT
© Georg Thieme Verlag Stuttgart ˙ New York

Bidentate Lewis Acids as Catalysts for the Activation of 1,2-Diazenes in Organic Synthesis

Hermann A. Wegner*, Simon N. Kessler
University of Basel, Department of Chemistry, St. Johanns-Ring 19, 4056 Basel, Switzerland
Fax: +41(61)2670976; e-Mail: hermann.wegner@unibas.ch;
Weitere Informationen

Publikationsverlauf

Received 3 September 2011
Publikationsdatum:
04. Januar 2012 (online)

   Lizenzen und Reprints Alle Artikel dieser Rubrik
Preview

Abstract

A new concept for the catalysis of the inverse-electron-demand Diels-Alder (IEDDA) reaction of 1,2-diazenes using bidentate Lewis acid was recently reported by our group. The general catalytic principle is based on the simultaneous coordination of the bidentate Lewis acid to the 1,2-diazene moiety, lowering the LUMO to facilitate the cycloaddition step. Extrusion of N2 regenerates the catalyst and after elimination the aromatic product is obtained. In this account the development of this new catalytic principle is described and put into the general context of Lewis acid catalysis.

1 Introduction

2 Interaction of Bidentate Lewis Acids with 1,2-Diazenes

3 Catalytic IEDDA Reaction of 1,2-Diazenes with a Bidentate Lewis Acid

3.1 The General Principle of Catalysis

3.2 Evaluation of the Concept by Calculations

3.3 Synthesis of the Bidentate Lewis Acid Catalyst

3.4 Characterization of the Bidentate Lewis Acid-1,2-Diazene Complex

3.5 Catalysis of the IEDDA Reaction of 1,2-Diazenes

3.6 General Trends

4 Conclusion

Key words

Lewis acids - catalysis - Diels-Alder reaction - boron - arenes

    References

  • 1 Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004. 
  • 2a Handbook of Metathesis   Grubbs RH. Wiley-VCH; Weinheim: 2003. 
  • 2b Metathesis in Natural Product Synthesis. Strategies, Substrates and Catalysts; Cossy J., Arseniyadis S., Meyer C.; Wiley-VCH: Weinheim, 2011
  • 3 Lewis Acids in Organic Synthesis   Yamamoto H. Wiley-VCH; Weinheim: 2000. 
  • 4 Inukai T. Kojima T. J. Org. Chem.  1966,  31:  1121 
    Suche in Google Scholar
  • 5 Biallas MJ. Shriver DF. J. Am. Chem. Soc.  1966,  88:  375 
    Suche in Google Scholar
  • 6 Wuest JD. Acc. Chem. Res.  1999,  32:  81 
    Suche in Google Scholar
  • 7 Grdeni ć D. Korpar-Č olig B. Sikirica M. Bruvo M.
    J. Organomet. Chem.  1982,  238:  327 
    Suche in Google Scholar
  • 8 Ooi T. Takahashi M. Maruoka K. J. Am. Chem. Soc.  1996,  118:  11307 
    Suche in Google Scholar
  • 9 Maruoka K. Catal. Today  2001,  66:  33 
    Suche in Google Scholar
  • 10a

    see ref. 9

  • 10b Maruoka K. Pure Appl. Chem.  2002,  74:  123 
    Suche in Google Scholar
  • 10c Li H. Marks TJ. Proc. Natl. Acad. Sci. U.S.A.  2006,  103:  15295 
    Suche in Google Scholar
  • For reviews, see:
  • 11a Taylor MS. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  1520 
    Suche in Google Scholar
  • 11b Connon SJ. Chem. Commun.  2008,  2499 
  • 11c Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal.  2006,  348:  999 
    Suche in Google Scholar
  • 11d Takemoto Y. Chem. Pharm. Bull.  2010,  58:  593 
    Suche in Google Scholar
  • 11e Pihko PM. Angew. Chem. Int. Ed.  2004,  43:  2062 
    Suche in Google Scholar
  • 11f Schreiner PR. Chem. Soc. Rev.  2003,  32:  289 
    Suche in Google Scholar
  • 12 Okino T. Hoashi Y. Takemoto Y. J. Am. Chem. Soc.  2003,  125:  12672 
    Suche in Google Scholar
  • 13 Hoashi Y. Okino T. Takemoto Y. Angew. Chem. Int. Ed.  2005,  44:  4032 
    Suche in Google Scholar
  • For reviews, see:
  • 14a Lee AY. Stewart JD. Clardy J. Ganem B. Chem. Biol.  1995,  2:  195 
    Suche in Google Scholar
  • 14b Ganem B. Angew. Chem., Int. Ed. Engl.  1996,  35:  936 
    Suche in Google Scholar
  • 15 Kessler SN. Wegner HA. Org. Lett.  2010,  12:  4062 
    Suche in Google Scholar
  • 16 Kessler SN. Neuburger M. Wegner HA. Eur. J. Org. Chem.  2011,  3238 
  • 17a Drew MGB. Yates PC. Troch-Grimshaw J. Lavery A. McKillop KP. Nelson SM. Nelson J.
    J. Chem. Soc., Dalton Trans.  1988,  347 
  • 17b Drew MGB. Yates PC. Paul BP. Nelson J. Inorg. Chim. Acta  1986,  118:  37 
    Suche in Google Scholar
  • 18 Xiao N. Xu Q. Sun J. Chen J. Dalton Trans.  2005,  3250 
  • 19 Austin M. Gebreyes K. Kuivila HG. Swami K. Zubieta JA. Organometallics  1987,  6:  834 
    Suche in Google Scholar
  • 20 Gabbai FP. Schier A. Riede J. Hynes MJ. Chem. Commun.  1998,  897 
  • 21 Isobe K. Okeya S. Meanwell NJ. Smith AJ. Adams H. Maitlis PM. J. Chem. Soc., Dalton Trans.  1984,  1215 
  • 22 Rashidi M. Nabavizadeh SM. Zare A. Jamali S. Puddephatt RJ. Inorg. Chem.  2010,  49:  8435 
    Suche in Google Scholar
  • 23 Jaska CA. Emslie DJH. Bosdet MJD. Piers WE. Sorensen TS. Parvez M. J. Am. Chem. Soc.  2006,  128:  10885 
    Suche in Google Scholar
  • 24 Lorbach A. Bolte M. Lerner H.-W. Wagner M. Chem. Commun.  2010,  46:  3592 
    Suche in Google Scholar
  • 25a Boger DL. Tetrahedron  1983,  39:  2869 
    Suche in Google Scholar
  • 25b Boger DL. Coleman RS. J. Org. Chem.  1984,  49:  2240 
    Suche in Google Scholar
  • 26 Turchi S. Nesi R. Giomi D. Tetrahedron  1998,  54:  1809 
    Suche in Google Scholar
  • 27 Gruseck U. Heuschmann M. Tetrahedron Lett.  1987,  28:  6027 
    Suche in Google Scholar
  • 28 Boger DL. Coleman RS. J. Am. Chem. Soc.  1987,  109:  2717 
    Suche in Google Scholar
  • 29 Bodwell GJ. Li J. Angew. Chem. Int. Ed.  2002,  41:  3261 
    Suche in Google Scholar
  • 30a Hartmann K.-P. Heuschmann M. Angew. Chem., Int. Ed. Engl.  1989,  28:  1267 
    Suche in Google Scholar
  • 30b Hartmann K.-P. Heuschmann M. Tetrahedron  2000,  56:  4213 
    Suche in Google Scholar
  • 31a Ernd M. Heuschmann M. Zipse H. Helv. Chim. Acta  2005,  88:  1491 
    Suche in Google Scholar
  • 31b Rooshenas P. Hof K. Schreiner P. Williams C. Eur. J. Org. Chem.  2011,  983 
  • 32 Bettinger HF. Filthaus M. J. Org. Chem.  2007,  72:  9750 
    Suche in Google Scholar
  • 33a Bader S. Kessler SN. Wegner HA. Synthesis  2010,  2759 
  • 33b Recently also a protocol accessing 1,2-bis(TMS)- benzene by using Rieke-Mg or Mg turnings in the presence of 1,2-dibromoethane as an entrainer was published: Lorbach A. Reus C. Bolte M. Lerner H.-W. Wagner M. Adv. Synth. Catal.  2010,  352:  3443 
    Suche in Google Scholar
  • 34 Kaufmann D. Chem. Ber./Recl.  1987,  120:  901 
    Suche in Google Scholar
  • 35 Schacht W. Kaufmann D. J. Organomet. Chem.  1987,  331:  139 
    Suche in Google Scholar
  • 36 Schulz H. Pritzkow H. Siebert W. Chem. Ber.  1991,  124:  2203 
    Suche in Google Scholar
  • 37 Uno H. Okada S. Suzuki H. Tetrahedron  1991,  47:  6231 
    Suche in Google Scholar
  • 38 Sauer J. Heldmann DK. Hetzenegger J. Krauthan J. Sichert H. Schuster J. Eur. J. Org. Chem.  1998,  2885