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Synlett 2011(6): 783-786  
DOI: 10.1055/s-0030-1259920
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Manganese(III)-Catalyzed Formal [3+2] Annulation of Vinyl Azides and β-Keto Acids for Synthesis of Pyrroles

Eileen Pei Jian Ng, Yi-Feng Wang, Shunsuke Chiba*
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, 21 Nanyang Link, 637371 Singapore
Fax: +6567911961; e-Mail: shunsuke@ntu.edu.sg;
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Publication History

Received 2 December 2010
Publication Date:
16 March 2011 (online)

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Abstract

Manganese(III)-catalyzed formal [3+2] annnulation of vinyl azides and β-keto acids has been developed for the synthesis of substituted NH pyrroles with a wide range of substituents.

Key words

manganese(III) catalysts - radical reactions - vinyl azides - β-keto acids - pyrroles

    References and Notes

  • For recent reviews, see:
  • 1a Walsh CT. Garneau-Tsodikova S. Howard-Jones AR. Nat. Prod. Rep.  2006,  23:  517 
    Search in Google Scholar
  • 1b Fürstner A. Angew. Chem. Int. Ed.  2003,  42:  3582 
    Search in Google Scholar
  • 1c Hoffmann H. Lindel T. Synthesis  2003,  1753 
  • 2a Hall A. Atkinson S. Brown SH. Chessell IP. Chowdhury A. Giblin GMP. Goldsmith P. Healy MP. Jandu KS. Johnson MR. Michel AD. Naylor A. Sweeting JA. Bioorg. Med. Chem. Lett.  2007,  17:  1200 
    Search in Google Scholar
  • 2b Bellina F. Rossi R. Tetrahedron  2006,  62:  7213 
    Search in Google Scholar
  • 2c Micheli F. Di Fabio R. Benedetti R. Capelli AM. Cavallini P. Cavanni P. Davalli S. Donati D. Feriani A. Gehanne S. Hamdan M. Maffeis M. Sabbatini FM. Tranquillini ME. Viziano MVA. Farmaco  2004,  59:  175 
    Search in Google Scholar
  • 2d Huffman JW. Curr. Med. Chem.  1999,  6:  705 
    Search in Google Scholar
  • 2e Roth BD. Blankley CJ. Chucholowski AW. Ferguson E. Hoefle ML. Ortwine DF. Newton RS. Sekerke CS. Sliskovic DR. Stratton CD. Wilson MW. J. Med. Chem.  1991,  34:  357 
    Search in Google Scholar
  • 3a Plitt P. Gross DE. Lynch VM. Sessler JL. Chem. Eur. J.  2007,  13:  1374 
    Search in Google Scholar
  • 3b Zhao W. Carreira EM. Chem. Eur. J.  2006,  12:  7254 
    Search in Google Scholar
  • 3c Gale PA. Acc. Chem. Res.  2006,  39:  465 
    Search in Google Scholar
  • 3d Nadeau JM. Swager TM. Tetrahedron  2004,  60:  7141 
    Search in Google Scholar
  • 3e Sessler JL. Camiolo S. Gale PA. Coord. Chem. Rev.  2003,  240:  17 
    Search in Google Scholar
  • 3f Yoon DW. Hwang H. Lee CH. Angew. Chem. Int. Ed.  2002,  41:  1757 
    Search in Google Scholar
  • 3g Seidel D. Lynch V. Sessler JL. Angew. Chem. Int. Ed.  2002,  41:  1422 
    Search in Google Scholar
  • 3h Miyaji H. Sato W. Sessler JL. Angew. Chem. Int. Ed.  2000,  39:  1777 
    Search in Google Scholar
  • 3i Depraetere S. Smet M. Dehaen W. Angew. Chem. Int. Ed.  1999,  38:  3359 
    Search in Google Scholar
  • For recent reviews on the synthesis of pyrroles, see:
  • 4a Estévez V. Villacampa M. Menéndez JC. Chem. Soc. Rev.  2010,  39:  4402 
    Search in Google Scholar
  • 4b Ferreira VF. de Souza M. Cunha AC. Pereira LOR. Ferreira MLG. Org. Prep. Proced. Int.  2001,  33:  411 
    Search in Google Scholar
  • 4c Balme G. Angew. Chem. Int. Ed.  2004,  43:  6238 
    Search in Google Scholar
  • 4d Joshi U. Pipelier M. Naud S. Dubreuil D. Curr. Org. Chem.  2005,  9:  261 
    Search in Google Scholar
  • 4e Patil NT. Yamamoto Y. ARKIVOC  2007,  (x):  121 
    Search in Google Scholar
  • 4f Schmuck C. Rupprecht D. Synthesis  2007,  3095 
  • For recent selected reports on the synthesis of polysubstituted pyrroles, see:
  • 5a Rakshit S. Patureau FW. Glorius F. J. Am. Chem. Soc.  2010,  132:  9585 
    Search in Google Scholar
  • 5b Morin MAT. St-Cyr DJ. Arndtsen BA. Org. Lett.  2010,  12:  4916 
    Search in Google Scholar
  • 5c Wang H.-Y. Mueller DS. Sachwani RM. Londino HN. Anderson LL. Org. Lett.  2010,  12:  2290 
    Search in Google Scholar
  • 5d Saito A. Konishi T. Hanzawa Y. Org. Lett.  2010,  12:  372 
    Search in Google Scholar
  • 5e Zhao X. Zhang E. Tu Y.-Q. Zhang Y.-Q. Yuan D.-Y. Cao K. Fan C.-A. Zhang F.-M. Org. Lett.  2009,  11:  4002 
    Search in Google Scholar
  • 5f Fu X. Chen J. Li G. Liu Y. Angew. Chem. Int. Ed.  2009,  48:  5500 
    Search in Google Scholar
  • 5g Saito A. Konishi T. Hanzawa Y. Org. Lett.  2009,  12:  372 
    Search in Google Scholar
  • 5h Lu Y. Arndtsen BA. Org. Lett.  2009,  11:  1369 
    Search in Google Scholar
  • 5i Liu W. Jiang H. Huang L. Org. Lett.  2009,  12:  312 
    Search in Google Scholar
  • 5j Kiren S. Hong X. Leverett CA. Padwa A. Org. Lett.  2009,  11:  1233 
    Search in Google Scholar
  • 5k Fontaine P. Masson G. Zhu J. Org. Lett.  2009,  11:  1555 
    Search in Google Scholar
  • 5l Davies PW. Martin N. Org. Lett.  2009,  11:  2293 
    Search in Google Scholar
  • 5m Aponick A. Li C.-Y. Malinge J. Marques EF. Org. Lett.  2009,  11:  4624 
    Search in Google Scholar
  • 5n Mizuno A. Kusama H. Iwasawa N. Angew. Chem. Int. Ed.  2009,  48:  8318 
    Search in Google Scholar
  • 5o Ackermann L. Sandmann R. Kaspar LT. Org. Lett.  2009,  11:  2031 
    Search in Google Scholar
  • 5p Lu Y. Arndtsen BA. Angew. Chem. Int. Ed.  2008,  47:  5430 
    Search in Google Scholar
  • 5q Cacchi S. Fabrizi G. Filisti E. Org. Lett.  2008,  10:  2629 
    Search in Google Scholar
  • 5r Attanasi OA. Favi G. Filippone P. Giorgi G. Mantellini F. Moscatelli G. Spinelli D. Org. Lett.  2008,  10:  1983 
    Search in Google Scholar
  • 5s St. Cyr DJ. Arndtsen BA. J. Am. Chem. Soc.  2007,  129:  12366 
    Search in Google Scholar
  • 5t Cadierno V. Gimeno J. Nebra N. Chem. Eur. J.  2007,  13:  9973 
    Search in Google Scholar
  • 5u Su S. Porco JA. J. Am. Chem. Soc.  2007,  129:  7744 
    Search in Google Scholar
  • 5v Martín R. Rodríguez Rivero M. Buchwald SL. Angew. Chem. Int. Ed.  2006,  45:  7079 
    Search in Google Scholar
  • 5w Crawley ML. Goljer I. Jenkins DJ. Mehlmann JF. Nogle L. Dooley R. Mahaney PE. Org. Lett.  2006,  8:  5837 
    Search in Google Scholar
  • 5x Hiroya K. Matsumoto S. Ashikawa M. Ogiwara K. Sakamoto T. Org. Lett.  2006,  8:  5349 
    Search in Google Scholar
  • 5y Binder JT. Kirsch SF. Org. Lett.  2006,  8:  2151 
    Search in Google Scholar
  • 5z Gorin DJ. Davis NR. Toste FD. J. Am. Chem. Soc.  2005,  127:  11260 
    Search in Google Scholar
  • For prior studies on iminyl radical formation from vinyl azides, see:
  • 6a Montevecchi PC. Navacchia ML. Spagnolo P. J. Org. Chem.  1997,  62:  5846 
    Search in Google Scholar
  • 6b Bamford AF. Cook MD. Roberts BP. Tetrahedron Lett.  1983,  24:  3779 
    Search in Google Scholar
  • For reviews of synthesis of azaheterocycles using iminyl radicals, see:
  • 7a Stella L. In Radicals in Organic Synthesis   Vol. 2:  Renaud P. Sibi MP. Wiley-VCH; Weinheim: 2001.  p.407-426  
    Search in Google Scholar
  • 7b Mikami T. Narasaka K. In Advances in Free Radical Chemistry   Vol. 2:  Zard SZ. JAI; Greenwich: 1999.  p.45-88  
    Search in Google Scholar
  • 7c Fallis AG. Brinza IM. Tetrahedron  1997,  53:  17543 
    Search in Google Scholar
  • 7d Zard SZ. Synlett  1996,  1148 
  • For our previous communications based on this concept for the synthesis of azaheterocycles, see:
  • 8a Wang Y.-F. Chiba S. J. Am. Chem. Soc.  2009,  131:  12570 
    Search in Google Scholar
  • 8b Wang Y.-F. Toh KK. Chiba S. Narasaka K. Org. Lett.  2008,  10:  5019 
    Search in Google Scholar
  • 9 Fortner KC. Shair MD. J. Am. Chem. Soc.  2007,  129:  1032 
    CrossrefPubMedSearch in Google Scholar
  • 10 Narasaka K. Miyoshi N. Iwakura K. Okauchi T. Chem. Lett.  1989,  18:  2169 
    Search in Google Scholar
  • 11 Mn(OAc)3, Mn(pic)3, and Mn(acac)3 possess different redox potentials, see: Richert SA. Tsang PKS. Sawyer DT. Inorg. Chem.  1988,  27:  1814 
    CrossrefSearch in Google Scholar
  • 12 For the addition of manganese(III) enolate to alkenes to give alkyl radicals, see: Snider BB. Patricia JJ. Kates SA. J. Org. Chem.  1988,  53:  2137 
    Search in Google Scholar
  • 13 For an example of addition of aminyl radicals to carbonyl groups, see: Kim S. Joe GH. Do JY. J. Am. Chem. Soc.  1993,  115:  3328 
    CrossrefSearch in Google Scholar
14

General Procedure for Mn(acac) 3 -Catalyzed Pyrrole Formation from Vinyl Azides and β-Keto Acids: To a solution of α-azido styrene (1a; 52.8 mg, 0.364 mmol) and 2-oxocyclohexanecarboxylic acid (2a; 155.2 mg, 1.09 mmol) in DMF (3.6 mL) was added Mn(acac)3 (12.8 mg, 0.0364 mmol) and the mixture was stirred for 5 h. The reaction mixture was quenched with a pH 9 ammonium buffer, and then extracted with Et2O (2 ×). The combined organic extracts were washed with brine, dried over MgSO4 and concentrated. Purification of the crude product by flash column chromatography (florisil; hexane-EtOAc = 97:3) afforded 3aa (59.5 mg, 0.302 mmol) in 83% yield.