Download PDF
Synthesis 2007(9): 1403-1411  
DOI: 10.1055/s-2007-966021
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Symmetrically and Unsymmetrically Substituted N,N′-Diaryl­imidazolin-2-ones by Copper-Catalyzed Arylamidation under Microwave-Assisted­ and Conventional Conditions

Thomas Hafner, Doris Kunz*
Ruprecht-Karls-Universität Heidelberg, Organisch-Chemisches Institut, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49(6221)544885; e-Mail: Doris.Kunz@oci.uni-heidelberg.de;
Further Information

Publication History

Received 21 July 2006
Publication Date:
18 April 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

A convenient synthesis of unsymmetrically substituted N,N′-diarylimidazolin-2-ones is reported. Starting from 2,2-dimethoxyethylamine, the first aryl group was introduced by reaction with arylisocyanate and subsequent cyclization to afford N-arylimidazolin-2-ones. The second arylation step was then accomplished by microwave-assisted copper-catalyzed arylamidation of the N-arylimidazolin-2-ones with a variety of aryliodides and arylbromides to give unsymmetrically substituted N,N′-diarylimidazolin-2-ones. Symmetrically substituted N,N′-diarylimidazolin-2-ones could also be prepared from imidazolin-2-one in a two-fold copper-catalyzed arylamidation, however, the nature of the substrate limits the use of this reaction.

Key words

amination - arylation - copper - homogeneous catalysis - heterocycles

    References

  • 1a Muchmore SW. Souers AJ. Akritopoulou-Zanze I. Chem. Biol. Drug Design.  2006,  67:  174 
    CrossrefGoogle Scholar
  • 1b Schwink L, Stengelin S, Gossel M, Boehme T, Hessler G, Rosse G, and Walser A. inventors; PCT Int. Appl. WO  2004011438.  ; Chem. Abstr. 2004, 140, 163866
    Crossref
  • 1c Wilde RG, Takasugi JJ, Hwang S, Welch EM, and Chen G. inventors; PCT Int. Appl. WO  2004009558.  ; Chem. Abstr. 2004, 140, 146137
    Crossref
  • 1d Himmelsbach F, Pieper H, Austel V, Linz G, Weisenberger J, Eisert W, and Mueller T. inventors; U.S. Patent US  5852192.  ; Chem. Abstr. 1999, 130, 665504
    Crossref
  • 1e Felix RA. inventors; U.S. Patent US  4724261.  ; Chem. Abstr. 1988, 108, 167475
    Crossref
  • 2a Tanaka K, and Doi M. inventors; Japan Patent JP  4343365.  ; Chem. Abstr. 1993, 118, 263846
  • 2b Klüpfel KW, Stumpf HR, Behmenburg H, Neugebauer W, Süs O, and Tomanek M. inventors; German Patent Appl. DE  1060713.  ; Chem. Abstr. 1961, 55, 110603
  • 3a Brazier SA. McCombie H. J. Chem. Soc.  1912,  101:  2352 
    CrossrefGoogle Scholar
  • 3b Schönherr HJ. Wanzlick HW. Chem. Ber.  1970,  103:  1037 
    CrossrefGoogle Scholar
  • 4 Watabe Y, Kondo T, and Watabe Y. inventors; Japan Patent JP  5004970.  ; Chem. Abstr. 1993, 118, 254934
  • 5 Lozanova K. Kalcheva V. Simov D. Chem. Heterocycl. Compd. (Engl. Transl.)  1988,  24:  1129 
    CrossrefGoogle Scholar
  • 6 Wendeborn S. Winkler T. Foisy I. Tetrahedron Lett.  2000,  41:  6387 
    CrossrefGoogle Scholar
  • 7a Mann G. Hartwig JF. Driver MS. Fernández-Rivas C. J. Am. Chem. Soc.  1998,  120:  827 
    CrossrefGoogle Scholar
  • 7b Yang BH. Buchwald SL. J. Organomet. Chem.  1999,  576:  125 
    CrossrefGoogle Scholar
  • 7c Shekhar S. Ryberg P. Hartwig JF. Mathew JS. Blackmond DG. Strieter ER. Buchwald SL. J. Am. Chem. Soc.  2006,  128:  3584 
    CrossrefGoogle Scholar
  • 8a Ullmann F. Ber. Dtsch. Chem. Ges.  1903,  36:  2382 
    CrossrefGoogle Scholar
  • 8b Goldberg I. Ber. Dtsch. Chem. Ges.  1906,  39:  1691 
    CrossrefGoogle Scholar
  • 8c Sugahara M. Ukita T. Chem. Pharm. Bull.  1997,  45:  719 
    CrossrefGoogle Scholar
  • 8d Strieter ER. Blackmond DG. Buchwald SL. J. Am. Chem. Soc.  2005,  127:  4120 
    CrossrefGoogle Scholar
  • 8e Haider J. Kunz K. Scholz U. Adv. Synth. Catal.  2004,  346:  717 
    CrossrefGoogle Scholar
  • 8f Beletskaya IP. Cheprakov AV. Coord. Chem. Rev.  2004,  248:  2337 
    CrossrefGoogle Scholar
  • For examples of palladium-catalyzed reactions with urea, see:
  • 9a Artamkina GA. Sergeev AG. Beletskaya IP. Tetrahedron Lett.  2001,  42:  4381 
    CrossrefGoogle Scholar
  • 9b Sergeev AG. Artamkina GA. Beletskaya IP. Tetrahedron Lett.  2003,  44:  4719 
    CrossrefGoogle Scholar
  • For examples of copper-catalyzed reactions with urea, see:
  • 9c Buchwald SL, Klapars A, Antilla JC, Job GE, Wolter M, Kwong FY, Nordmann G, and Hennessy EJ. inventors; PCT Int. Appl. WO  02085838.  ; Chem. Abstr. 2002, 137, 352492
    CrossrefGoogle Scholar
  • 9d Nandakumar MV. Tetrahedron Lett.  2004,  45:  1989 
    CrossrefGoogle Scholar
  • 9e Trost BM. Styles DT. Org. Lett.  2005,  7:  2117 
    CrossrefGoogle Scholar
  • For examples with benzimidazolinones, see:
  • 9f Ward RE. Meyer TY. Macromolecules  2003,  36:  4368 
    CrossrefGoogle Scholar
  • 10 Yang GX. Chang LL. Truong Q. Doherty GA. Magriotis PA. de Laszlo SE. Li B. MacCoss M. Kidambi U. Egger LA. McCauley E. Van Riper G. Mumford RA. Schmidt JA. Hagmann WK. Bioorg. Med. Chem. Lett.  2002,  12:  1497 
    CrossrefGoogle Scholar
  • 11a Mann G. Hartwig JF. Driver MS. Fernández-Rivas C. J. Am. Chem. Soc.  1998,  120:  827 
    CrossrefPubMedGoogle Scholar
  • 11b Grasa GA. Viciu MS. Huang J. Nolan SP. J. Org. Chem.  2001,  66:  7729 
    CrossrefPubMedGoogle Scholar
  • 11c Vargas VC. Rubio RJ. Hollis TK. Salcido ME. Org. Lett.  2003,  5:  4847 
    CrossrefPubMedGoogle Scholar
  • 11d Klapars A. Antilla JC. Huang X. Buchwald SL. J. Am. Chem. Soc.  2001,  123:  7727 
    CrossrefPubMedGoogle Scholar
  • 11e Antilla JC. Baskin JM. Barder TE. Buchwald SL. J. Org. Chem.  2004,  69:  5578 
    CrossrefPubMedGoogle Scholar
  • 12 Kiyomori A. Marcoux J.-F. Buchwald SL. Tetrahedron Lett.  1999,  40:  2657 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 13a Nilsson P. Olofsson K. Larhed M. Top. Curr. Chem.  2006,  266:  103 
    CrossrefGoogle Scholar
  • 13b Wan Y. Alterman M. Hallberg A. Synthesis  2002,  1597 
    CrossrefGoogle Scholar
  • 13c Yadav LDS. Yadav BS. Rai VK. Synthesis  2006,  1868 
    CrossrefGoogle Scholar
  • 13d Lange JHM. Hofmeyer LJF. Hout FAS. Osnabrug SJM. Verveer PC. Kruse CG. Feenstra RW. Tetrahedron Lett.  2002,  43:  1101 
    CrossrefGoogle Scholar
  • 13e For a review involving urea, see: Wannberg J. Dallinger D. Kappe CO. Larhed M. J. Comb. Chem.  2005,  7:  574 
    CrossrefGoogle Scholar
  • 14 Forrest TP. Dauphinee GA. Chen FMF. Can. J. Chem.  1974,  52:  2725 
    CrossrefGoogle Scholar
  • 16 Marckwald W. Ber. Dtsch. Chem. Ges.  1892,  25:  2354 
    CrossrefGoogle Scholar
  • 17 Duchinsky R. Dolan LA. J. Am. Chem. Soc.  1946,  68:  2351 
    Google Scholar
  • 18 Golovko VV. Statsenskaya AI. Baskakov YA. Putsykin YG. Chem. Heterocycl. Compd.  1986,  22:  1084 
    CrossrefGoogle Scholar
  • 19 Cortes S. Liao Z.-K. Watson D. Kohn H. J. Med. Chem.  1985,  28:  601 
    CrossrefGoogle Scholar
15

Leadbeater has shown that when the Powermax cooling function is used, the standard IR sensor does not give accurate temperature measurements. In DMSO at a nominal temperature of 100 °C, the actual temperature was 20 °C higher, whereas in hexane, the actual temperature was 20 °C lower. We have used dioxane so the respective effects could level out, however the real temperature could vary by about ±20 °C from the given value in the case of the experiments reported in Table [3] .