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Synthesis 2004(5): 761-764  
DOI: 10.1055/s-2004-815984
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart · New York

Rearrangement of Cyclic Allenes via 1,2-Dehydro[10]annulenes: Intramolecular Dehydro Diels-Alder of 3-(Trimethylsilyl)propiolamides

David Rodríguez, Luis Castedo, Domingo Domínguez, Carlos Saá*
Departamento de Química Orgánica e Unidade Asociada ó CSIC, Facultade de Química, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain
Fax: +34(981)595012; e-Mail: qocsaa@usc.es;
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Publication History

Received 30 January 2004
Publication Date:
24 February 2004 (online)

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Abstract

Rearrangements of cyclic allenes giving benzo[e]isoindoles were observed when studying intramolecular dehydro Diels-Alder reactions of N-[(3-aryl)propargyl]-3-(trimethylsilyl)propiol­amides.

Key words

allenes - Diels-Alder reactions - annulenes - amides - alkynes

    References

  • 1a Michael A. Bucher JE. Chem. Ber.  1895,  28:  2511 
    Google Scholar
  • 1b Danheiser RL. Gould A. Fernández de la Pradilla R. Helgason AL. J. Org. Chem.  1994,  59:  5514 
    Google Scholar
  • 1c Burrell RC. Daoust KJ. Bradley AZ. DiRico KJ. Johnson RP. J. Am. Chem. Soc.  1996,  118:  4218 
    Google Scholar
  • 1d Schmittel M. Strittmatter M. Schemk WA. Hagel M. Z. Naturforsch., B: Chem. Sci.  1998,  53:  1015 
    Google Scholar
  • 2 Johnson RP. Chem. Rev.  1989,  89:  1111 
    CrossrefGoogle Scholar
  • 3a Rodríguez D. Navarro A. Castedo L. Domínguez D. Saá C. Org. Lett.  2000,  2:  1497 
    Google Scholar
  • 3b Rodríguez D. Navarro-Vázquez A. Castedo L. Domínguez D. Saá C. J. Org. Chem.  2003,  68:  1938 
    Google Scholar
  • 4 Rodríguez D. Navarro-Vázquez A. Castedo L. Domínguez D. Saá C. J. Am. Chem. Soc.  2001,  123:  9178 
    CrossrefGoogle Scholar
  • 5 Atienza C. Mateo C. de Frutos . Echavarren AM. Org. Lett.  2001,  3:  153 
    CrossrefPubMedGoogle Scholar
  • 6 Rodríguez D. Navarro-Vázquez A. Castedo L. Domínguez D. Saá C. Tetrahedron Lett.  2002,  43:  2717 
    Google Scholar
  • 7 For synthesis of unsubstituted propiolamides, see: Coppola GM. Damon RE. Synth. Commun.  1993,  23:  2003 
    CrossrefGoogle Scholar
8

Compounds 6a-c were also rather unstable, decomposing rapidly under acidic conditions. In fact, under the Pd-catalyzed coupling conditions both 5 and 6 decomposed slowly, making it necessary to optimize the reaction time. Long reaction times did not afford the desired products.

9

Et3N favours isomerization of the initial cyclic allene to the corresponding linear aromatic product, thus precluding its rearrangement; see ref. [4]

10

Minor amounts of the benzo[f]isoindol-1-one 2b (10%) and its desilylated derivative (not shown, 9%) were also observed in this case.

11

The E,Z-nomenclature here is correct for 9a and 10a. The nomenclature for 9b (R = OMe) and 9c (R = NO2) should be 5Z,7E; the nomenclature for 10b (R = OMe) and 10c (R = NO2) should be 5E,7Z.