Download PDF
Synlett 2009(17): 2844-2848  
DOI: 10.1055/s-0029-1217982
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Rhodium N-Heterocyclic Carbene Complexes as Effective Catalysts for [2+2+2]-Cycloaddition Reactions

Iván González, Anna Pla-Quintana, Anna Roglans*
Department of Chemistry, University of Girona, Campus de Montilivi, s/n. 17071 Girona, Spain
Fax: +34(972)418150; e-Mail: anna.roglans@udg.edu;
Further Information

Publication History

Received 1 July 2009
Publication Date:
24 September 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

Rhodium complexes of N-heterocyclic carbenes (NHC) [RhCl(cod)(NHC)], [cod = 1,5-cyclooctadiene, NHC = 1,3-diisopropylimidazolin-2-ylidene, and NHC = 1,3-dimesitylimidazolin-2-ylidene] are tested for intra- and partially intramolecular [2+2+2]-cycloaddition reactions demonstrating their effectiveness in this kind of process. This is the first use of a rhodium-NHC complex in a [2+2+2]-cycloaddition reaction of three alkynes. ESI-MS has been used to detect oxidative addition intermediates using rhodium NHC as the catalytic system.

Key words

cycloadditions - rhodium - carbenes - homogenous catalysis - polycycles

    References and Notes

  • For recent reviews, see:
  • 1a Saito S. Yamamoto Y. Chem. Rev.  2000,  100:  2901 
    Google Scholar
  • 1b Varela JA. Saá C. Chem. Rev.  2003,  103:  3787 
    Google Scholar
  • 1c Yamamoto Y. Curr. Org. Chem.  2005,  9:  503 
    Google Scholar
  • 1d Kotha S. Brahmachary E. Lahiri K. Eur. J. Org. Chem.  2005,  4741 
    Google Scholar
  • 1e Chopade PR. Louie J. Adv. Synth. Catal.  2006,  348:  2307 
    Google Scholar
  • 1f Gandon V. Aubert C. Malacria M. Chem. Commun.  2006,  2209 
    Google Scholar
  • 1g Heller B. Hapke M. Chem. Soc. Rev.  2007,  36:  1085 
    Google Scholar
  • 1h Varela JA. Saá C. Synlett  2008,  2571 
    Google Scholar
  • 1i Shibata T. Tsuchikama K. Org. Biomol. Chem.  2008,  6:  1317 
    Google Scholar
  • 1j Galan BR. Rovis T. Angew. Chem. Int. Ed.  2009,  2830 
    Google Scholar
  • 2 Modern Rhodium-Catalyzed Organic Reactions   Evans PA. Wiley-VCH; Weinheim: 2005. 
    Google Scholar
  • 3a Baik M.-H. Baum EW. Burland MC. Evans PA. J. Am. Chem. Soc.  2005,  127:  1602 
    Google Scholar
  • 3b Evans PA. Baum EW. Fazal AN. Pink M. Chem. Commun.  2005,  63 
    Google Scholar
  • 4 Lee SI. Park SY. Park JH. Jung IG. Choi SY. Chung YK. J. Org. Chem.  2006,  71:  91 
    Google Scholar
  • 5 Peng HM. Webster RD. Li X. Organometallics  2008,  27:  4484 
    CrossrefGoogle Scholar
  • 6a Tekavec TN. Louie J. J. Org. Chem.  2008,  73:  2641 
    Google Scholar
  • 6b Tekavec TN. Louie J. Org. Lett.  2005,  7:  4037 
    Google Scholar
  • 7a Duong HA. Cross MJ. Louie J. J. Am. Chem. Soc.  2004,  126:  11438 
    Google Scholar
  • 7b Duong HA. Louie J. J. Organomet. Chem.  2005,  690:  5098 
    Google Scholar
  • 8 McCormick MM. Duong HA. Zuo G. Louie J. J. Am. Chem. Soc.  2005,  127:  5030 
    Google Scholar
  • 9a Louie J. Gibby JE. Farnworth MV. Tekavec TN. J. Am. Chem. Soc.  2002,  124:  15188 
    Google Scholar
  • 9b Tekavec TN. Arif AM. Louie J. Tetrahedron  2004,  60:  7431 
    Google Scholar
  • 10a Saino N. Kogure K. Okamoto S. Org. Lett.  2005,  7:  3065 
    Google Scholar
  • 10b Saino N. Kogure D. Kase K. Okamoto S. J. Organomet. Chem.  2006,  691:  3129 
    Google Scholar
  • 11 Geny A. Gaudrel S. Slowinski F. Amatore M. Chouraqui G. Malacria M. Aubert C. Gandon V. Adv. Synth. Catal.  2009,  351:  271 
    Google Scholar
  • 12 Seayad AM. Selvakumar K. Ahmed M. Beller M. Tetrahedron Lett.  2003,  44:  1679 
    Google Scholar
  • 13 Frey GD. Rentzsch CF. Preysing D. Scherg T. Mühlhofer M. Herdtwech E. Herrmann WA. J. Organomet. Chem.  2006,  691:  5725 
    CrossrefGoogle Scholar
  • 14a Pla-Quintana A. Roglans A. Torrent A. Moreno-Mañas M. Benet-Buchholz J. Organometallics  2004,  23:  2762 
    Google Scholar
  • 14b Torrent A. González I. Pla-Quintana A. Roglans A. Moreno-Mañas M. Parella T. Benet-Buchholz J. J. Org. Chem.  2005,  70:  2033 
    Google Scholar
  • 14c González I. Bouquillon S. Roglans A. Muzart J. Tetrahedron Lett.  2007,  48:  6425 
    Google Scholar
  • 14d Brun S. Garcia L. González I. Torrent A. Dachs A. Pla-Quintana A. Parella T. Roglans A. Chem. Commun.  2008,  4339 
    Google Scholar
  • 14e Dachs A. Torrent A. Roglans A. Parella T. Osuna S. Solà M. Chem. Eur. J.  2009,  15:  5289 
    Google Scholar
  • For recent examples of air-tolerant Ru- and Co-catalyzed [2+2+2] cycloadditions, respectively, see:
  • 15a Adriaenssens L. Severa L. Šálová T. Císařová I. Pohl R. Šaman D. Rocha SV. Finney NS. Pospíšil L. Slavíček P. Tepl F. Chem. Eur. J.  2009,  15:  1072 
    Google Scholar
  • 15b Geny A. Agenet N. Iannazzo L. Malacria M. Aubert C. Gandon V. Angew. Chem. Int. Ed.  2009,  48:  1810 
    Google Scholar
  • 16 Electrospray Ionization Mass Spectrometry, Fundamentals, Instrumentation and Applications   Cole RB. Wiley; New York: 1997. 
    Google Scholar
  • 17a Santos LS. Knaack L. Metzger JO. Int. J. Mass Spectrom.  2005,  246:  84 
    Google Scholar
  • 17b Eberlin MN. J. Mass Spectrom.  2006,  41:  141 
    Google Scholar
  • For selected references, see:
  • 18a Müller E. Synthesis  1974,  761 
    Google Scholar
  • 18b Mague JT. Inorg. Chem.  1970,  9:  1610 
    Google Scholar
  • 18c Mague JT. Inorg. Chem.  1973,  12:  2649 
    Google Scholar
  • 18d Gastinger RG. Rausch MD. Sullivan DA. Palenik GJ. J. Organomet. Chem.  1976,  117:  355 
    Google Scholar
  • 18e Iglesias M. del Pino C. Ros J. García Blanco S. Carrera SM. J. Organomet. Chem.  1988,  338:  89 
    Google Scholar
  • 18f Bianchini C. Caulton KG. Chardon C. Eisenstein O. Folting K. Johnson TJ. Meli A. Peruzzini M. Rauscher DJ. Streib WE. Vizza F. J. Am. Chem. Soc.  1991,  113:  5127 
    Google Scholar
  • 18g Bianchini C. Masi D. Meli A. Peruzzini M. Vacca A. Organometallics  1991,  10:  636 
    Google Scholar
  • 18h Bianchini C. Meli A. Peruzzini M. Vacca A. Vizza F. Organometallics  1991,  10:  645 
    Google Scholar
  • 18i Rourke JP. Batsanov AS. Howard JAK. Marder TB. Chem. Commun.  2001,  2626 
    Google Scholar
  • 18j Nishiyama H. Niwa E. Inoue T. Ishima Y. Aoki K. Organometallics  2002,  21:  2572 
    Google Scholar
  • 18k Xue P. Sung HSY. Williams ID. Jia G. J. Organomet. Chem.  2006,  691:  1945 
    Google Scholar