Download PDF
Synlett 2011(19): 2815-2818  
DOI: 10.1055/s-0031-1289566
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Pyrrole Synthesis via Silaphenylmercuric Triflate Catalyzed Cyclization of Homopropargyl Azides

Hirofumi Yamamoto*, Ikuo Sasaki, Mizuho Mitsutake, Ayumi Karasudani, Hiroshi Imagawa, Mugio Nishizawa
Faculty of Pharmaceutical Sciences, Tokushima Bunri University, Yamashiro-cho, Tokushima 770-8514, Japan
Fax: +81(88)6553051; e-Mail: hirofumi@ph.bunri-u.ac.jp;
Further Information

Publication History

Received 3 August 2011
Publication Date:
09 November 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

A mixture of phenylmercuric acetate and trifluoromethanesulfonic acid or silica gel supported phenylmercuric tri­fluoromethanesulfonate (silaphenyl mercuric triflate) efficiently catalyzed the formation of pyrroles from homopropargyl azide derivatives. The reactions proceed using 20 mol% of the heterogeneous catalyst with yields of isolated pyrroles ranging from 74% to 99%.

Key words

cyclization - heterocycles - heterogeneous catalysis - azides - alkynes

    References and Notes

  • 1a Jones A. Pyrroles   Jones RA. Wiley; New York: 1990.  p.105 
    Google Scholar
  • 1b Sundberg RJ. Comprehensive Heterocyclic Chemistry II   Vol. 2:  Katritzky AR. Rees CW. Scriven EFV. Elsevier; Oxford: 1996.  p.119 
    Google Scholar
  • 1c Eicher T. Hauptmann S. Speicher A. The Chemistry of Heterocycles   2nd ed.:  Wiley-VCH; Weinheim: 2003.  p.97 
    Google Scholar
  • 1d Fan H. Peng J. Hamann MT. Hu J.-F. Chem. Rev.  2008,  108:  264 
    Google Scholar
  • 2a Patil NT. Yamamoto Y. Chem. Rev.  2008,  108:  3395 
    Google Scholar
  • 2b Patil NT. Yamamoto Y. ARKIVOC  2007,  (x):  121 
    Google Scholar
  • 3a Knorr L. Ber. Dtsch. Chem. Ges.  1884,  17:  1635 
    Google Scholar
  • 3b Paal C. Ber. Dtsch. Chem. Ges.  1884,  17:  2756 
    Google Scholar
  • 3c Amarnath V. Anthony DC. Amarnath K. Valentine WM. J. Org. Chem.  1991,  56:  6924 
    Google Scholar
  • 3d Pridmore SJ. Slatford PA. Taylor JE. Whittlesey MK. Williams JMJ. Tetrahedron  2009,  65:  8981 
    Google Scholar
  • 3e Azizi N. Khajeh-Amiri A. Ghafuri H. Bolourtchian M. Saidi MR. Synlett  2009,  2245 
    Google Scholar
  • 3f Rivera S. Bandyopadhyay D. Banik BK. Tetrahedron Lett.  2009,  50:  5445 
    Google Scholar
  • 3g Chen J. Wu H. Zheng Z. Jin C. Zhang X. Su W. Tetrahedron Lett.  2006,  47:  5383 
    Google Scholar
  • 4 Hantzch A. Ber. Dtsch. Chem. Ges.  1890,  23:  1474 
    Google Scholar
  • 5a Trost BM. Doherty GA. J. Am. Chem. Soc.  2000,  122:  3801 
    Google Scholar
  • 5b Muchowski JM. Adv. Med. Chem.  1992,  1:  109 
    Google Scholar
  • 5c Xia M. Huang G. J. Org. Chem.  2010,  75:  7842 
    Google Scholar
  • 6 Gorin DJ. Davis NR. Toste FD. J. Am. Chem. Soc.  2005,  127:  11260 
    Google Scholar
  • 7a Reddy VP. Kumar AV. Rao KR. Tetrahedron Lett.  2011,  52:  777 
    Google Scholar
  • 7b Sharma R. Chouhan M. Sood D. Nair VA. Appl. Organomet. Chem.  2011,  25:  305 
    Google Scholar
  • 7c Rakshit S. Patureau FW. Glorius F. J. Am. Chem. Soc.  2010,  132:  9585 
    Google Scholar
  • 7d Ribeiro Laia FM. Cardoso AL. Beja AM. Silva MR. Pinho e Melo TMVD. Tetrahedron  2010,  66:  8815 
    Google Scholar
  • 7e Queiroz M.-JRP. Begouin A. Pereira G. Ferreira PMT. Tetrahedron  2008,  64:  10714 
    Google Scholar
  • 7f Oda M. Fukuchi Y. Ito S. Thanh NC. Kuroda S. Tetrahedron Lett.  2007,  48:  9159 
    Google Scholar
  • 7g Martin R. Rivero MR. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  7079 
    Google Scholar
  • 7h Harrison TJ. Kozak JA. Corbella-Pané M. Dake GR. J. Org. Chem.  2006,  71:  4525 
    Google Scholar
  • 7i Nishino F. Miki K. Kato Y. Ohe K. Uemura S. Org. Lett.  2003,  5:  2615 
    Google Scholar
  • 7j Ranu BC. Dey SS. Tetrahedron Lett.  2003,  44:  2865 
    Google Scholar
  • 7k Utimoto K. Miwa H. Nozaki H. Tetrahedron Lett.  1981,  22:  4277 
    Google Scholar
  • 8 Hiroya K. Matsumoto S. Ashikawa M. Ogiwara K. Sakamoto T. Org. Lett.  2006,  8:  5349 
    Google Scholar
  • 9 Wyrūbek P. Sniady A. Bewick N. Li Y. Mikus A. Wheeler KA. Dembinski R. Tetrahedron  2009,  65:  1268 
    Google Scholar
  • 10 Nishizawa M. Skwarczynski M. Imagawa H. Sugihara T. Chem. Lett.  2002,  12 
    Google Scholar
  • 11 Nishizawa M. Imagawa H. Yamamoto H. Org. Biomol. Chem.  2010,  8:  511 
    Google Scholar
  • 12 Yamamoto H. Sasaki I. Namba K. Imagawa H. Nishizawa M. Org. Lett.  2007,  9:  1399 
    Google Scholar
  • 14 Yamamoto H. Sasaki I. Hirai Y. Namba K. Imagawa H. Nishizawa M. Angew. Chem. Int. Ed.  2009,  48:  1244 
    Google Scholar
  • 15a Rahmatpour A. Aalaie J. Heteroat. Chem.  2011,  22:  85 
    Google Scholar
  • 15b Veisi H. Tetrahedron Lett.  2010,  51:  2109 
    Google Scholar
  • 15c Kumar MA. Krishna AB. Babu BH. Reddy CB. Reddy CS. Synth. Commun.  2008,  38:  3456 
    Google Scholar
  • 15d Nad S. Roler S. Haag R. Breinbauer R. Org. Lett.  2006,  8:  403 
    Google Scholar
  • 15e Curini M. Montanari F. Rosati O. Lioy E. Margarita R. Tetrahedron Lett.  2003,  44:  3923 
    Google Scholar
13

When the cyclization reaction of 1 with Hg(OTf)2 was quenched using Et3N and NaCl at -20 ˚C, the formation of pyrrolic mercury chloride corresponds to 7 was confirmed by ¹H NMR spectroscopy. However, pyrrolic mercury chloride was unstable under acidic conditions. During column chromatography on silica gel pyrrolic mercury chloride decomposed into 2.

16

Preparation of Silaphenylmercuric Triflate (10) and a Typical Experimental Procedure for a Silaphenyl-mercuric Triflate Catalyzed Cyclization
To a suspension of dried silaphenylmercuric acetate 9 (0.2 mmol/g, 500 mg, 0.1 mmol) in MeNO2 (5 mL) was added TfOH (17.4 µL, 0.2 mmol), and the mixture was stirred for 10 min at r.t. The filtered residue was washed with MeNO2 (10 mL) and dried to give silaphenylmercuric triflate 10. Next, MeNO2 (4 mL) and prepared 10 were added to a dried two-neck flask. To the stirred suspension of 10 was added a solution of 1 (86 mg, 0.5 mmol) in MeNO2 (1 mL) at r.t. under argon. The mixture was stirred at r.t. for 5 min, and the catalyst was then removed by filtration and washed with MeNO2 (10 mL). The combined filtrates were concentrated under reduced pressure. Purification by column chromatog-raphy on silica gel using hexane and EtOAc (10:1) gave pyrrole 2 (70 mg, 97%).

17

In all cases (Table  [³] ), recovery of 10 was between 99.29% and 99.89%.