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Synlett 2010(4): 529-534  
DOI: 10.1055/s-0029-1219340
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

The 2-(2-Azidoethyl)cycloalkanone Strategy for Bridged Amides and Medium-Sized Cyclic Amine Derivatives in the Aubé-Schmidt Reaction

Fraser Macleod, Stuart Lang, John A. Murphy*
WestCHEM, Dept. of Pure and Applied Chemistry, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, UK
Fax: +44(141)5484822; e-Mail: John.Murphy@strath.ac.uk;
Further Information

Publication History

Received 10 November 2009
Publication Date:
19 January 2010 (online)

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Abstract

2-(2-Azidoethyl)cycloalkanones afford bridged lactams in the Aubé-Schmidt reaction, sometimes in excellent yield, and solvolysis yields derivatives of medium-ring amines. Attempts to divert the Schmidt reaction with an arene-mediated fragmentation of the normal Schmidt intermediate have led to an initial example.

Key words

Aubé - Schmidt - rearrangement - azide - heterocycle - bridged amide - medium-ring amine - medium-ring amide

    References and Notes

  • 1a Aubé J. Milligan GL. J. Am. Chem. Soc.  1991,  113:  8965 
    Google Scholar
  • 1b Milligan GL. Mossman CJ. Aubé J. J. Am. Chem. Soc.  1995,  117:  10449 
    Google Scholar
  • 1c Huh CW. Somal GK. Katz CE. Pei H. Zeng Y. Douglas JT. Aubé J. J. Org. Chem.  2009,  74:  7618 
    Google Scholar
  • 1d See also: Kumar PS. Kapat A. Baskaran S. Tetrahedron Lett.  2008,  49:  1241 
    Google Scholar
  • 2a Pearson WH. Hutta DA. Fang WK. J. Org. Chem.  2000,  65:  8326 
    Google Scholar
  • 2b Pearson WH. Schkeryantz JM. Tetrahedron Lett.  1992,  33:  5291 
    Google Scholar
  • 2c Pearson WH. Walavalkar R. Schkeryantz JM. Fang WK. Blickensdorf JD. J. Am. Chem. Soc.  1993,  115:  10183 
    Google Scholar
  • 2d See also: Reddy PG. Baskaran S. J. Org. Chem.  2004,  69:  3093 
    Google Scholar
  • 2e Kapat A. Nyfeler E. Giuffredi GT. Renaud P. J. Am. Chem. Soc.  2009,  131:  DOI: 10.1021/ja908933s 
    Google Scholar
  • 3 Schmidt KF. Ber. Dtsch. Chem. Ges.  1924,  57:  704 
    CrossrefGoogle Scholar
  • For reviews, see:
  • 4a Lang S. Murphy JA. Chem. Soc. Rev.  2006,  35:  146 
    Google Scholar
  • 4b Nyfeler E. Renaud P. Chimia  2006,  60:  276 
    Google Scholar
  • 4c Grecian S. Aubé J. In Organic Azides: Synthesis and Applications   Bräse S. Banert K. Wiley-VCH; Weinheim: 2009.  p.191 
    Google Scholar
  • 4d Bräse S. Gil C. Knepper K. Zimmermann V. Angew. Chem. Int. Ed.  2005,  44:  5188 
    Google Scholar
  • 5 Lee HL. Aubé J. Tetrahedron  2007,  63:  9007 
    CrossrefGoogle Scholar
  • 6a Yao L. Aubé J. J. Am. Chem. Soc.  2007,  129:  2766 
    Google Scholar
  • 6b Ribelin T. Katz CE. English DG. Smith S. Manukyan AK. Day VW. Neuenswander B. Poutsma JL. Aubé J. Angew. Chem. Int. Ed.  2008,  47:  6233 
    Google Scholar
  • 6c Katz CE. Aubé J. J. Am. Chem. Soc.  2003,  125:  13948 
    Google Scholar
  • 7 Katz CE. Ribelin T. Withrow D. Basseri Y. Manukyan AK. Bermudez A. Nuera CG. Day VW. Powell DR. Poutsma JL. Aubé J. J. Org. Chem.  2008,  73:  3318 
    CrossrefGoogle Scholar
  • 8 Szostak M. Yao L. Aubé J. Org. Lett.  2009,  11:  4386 
    CrossrefGoogle Scholar
  • 9 Tani K. Stoltz BM. Nature (London)  2006,  441:  731 
    CrossrefGoogle Scholar
  • 10 Evans PA. Holmes AB. Tetrahedron  1991,  47:  9131 
    CrossrefGoogle Scholar
  • 11a Lei Y. Wrobleski AD. Golden JE. Powell DR. Aubé J. J. Am. Chem. Soc.  2005,  127:  4552 
    Google Scholar
  • 11b Szostak M. Aubé J. Org. Lett.  2009,  11:  3878 
    Google Scholar
  • 11c Szostak M. Yao L. Aubé J. J. Org. Chem.  2009,  74:  1869 
    Google Scholar
  • 12 Iyengar R. Schildknegt K. Aubé J. Org. Lett.  2000,  2:  1625 
    CrossrefGoogle Scholar
  • 13 For an alternative recent fragmentation route to macrocyclic amides, see: Murphy JA. Mahesh M. McPheators G. Anand RV. McGuire TM. Carling R. Kennedy AR. Org. Lett.  2007,  9:  3233 
    CrossrefGoogle Scholar
  • 14a Corr M. Gibson K. Kennedy AR. Murphy JA. J. Am. Chem. Soc.  2009,  131:  9174 
    Google Scholar
  • 14b Corr MJ. Roydhouse MD. Gibson KF. Zhou S.-Z. Kennedy AR. Murphy JA. J. Am. Chem. Soc.  2009,  131:  DOI: 10.1021/ja908191k 
    Google Scholar
  • 15 Benchekroun-Mounir N. Dugat D. Gramain J.-C. Husson H.-P. J. Org. Chem.  1993,  58:  6457 
    CrossrefGoogle Scholar
  • 16 For interception of alternative azide rearrangements by arenes, see: Lang S. Kennedy AR. Murphy JA. Payne AH. Org. Lett.  2003,  5:  3655 
    CrossrefGoogle Scholar
  • 17 Khoukhi M. Vaultier M. Carrié R. Tetrahedron Lett.  1986,  27:  1031 
    CrossrefGoogle Scholar
  • 18a Corey EJ. Enders D. Chem. Ber.  1978,  111:  1337 
    Google Scholar
  • 18b Corey EJ. Enders D. Chem. Ber.  1978,  111:  1362 
    Google Scholar
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These compounds were isolated as single isomers. The most likely stereochemistry of alkylation of the decalone enolate would afford 70 and methanolysis would convert this into 71.