Download PDF
Synlett 2012(1): 62-65  
DOI: 10.1055/s-0030-1260334
CLUSTER
© Georg Thieme Verlag Stuttgart ˙ New York

Enantioselective 1,3-Dipolar Cycloadditions of Azlactones and Electrophilic Alkenes Catalyzed by Dimeric BinapAuTFA Complexes

María Martín-Rodríguez, Carmen Nájera*, José M. Sansano*
Departamento de Química Orgánica e Instituto de Síntesis Orgánica (ISO), Facultad de Ciencias, Universidad de Alicante, 03080 Alicante, Spain
Fax: +34(965)903549; e-Mail: cnajera@ua.es; e-Mail: jmsansano@ua.es;
Further Information

Publication History

Received 21 July 2011
Publication Date:
27 September 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

Glycine-derived azlactones react with maleimides using (S)- or (R)-dimeric BinapAuTFA complexes affording the corresponding cycloadducts in good yields and high enantioselections (up to 99% ee). The intermediate carboxylic acids are treated with trimethylsilyldiazomethane and isolated as Δ¹-pyrroline methyl esters. These cycloadducts are transformed into exo-proline derivatives by reduction with NaBH3CN in acidic media. On the other hand, N-benzoylalanine-derived oxazolone reacts with tert-butyl acrylate providing the cycloadduct with the ester group at the 3-position with a trans-relative configuration with respect to the methyl ester group.

Key words

gold - Binap - cycloaddition - azomethine ylides - asymmetric catalysis

    References and Notes

  • For recent reviews about general 1,3-DC, see:
  • 1a Padwa A. Pearson WH. In Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Towards Heterocycles and Natural Products   John Wiley & Sons; New Jersey: 2003. 
    Google Scholar
  • 1b Nájera C. Sansano JM. Curr. Org. Chem.  2003,  7:  1105 
    Google Scholar
  • 1c Nair V. Suja TD. Tetrahedron  2007,  63:  12247 
    Google Scholar
  • 1d Padwa A. Bur SK. Tetrahedron  2007,  63:  5341 
    Google Scholar
  • 1e Pellissier H. Tetrahedron  2007,  63:  3235 
    Google Scholar
  • For reviews dealing with enantioselective 1,3-DC, see:
  • 2a Nájera C. Sansano JM. Top. Heterocycl. Chem.  2008,  12:  117 
    Google Scholar
  • 2b Stanley LM. Sibi MP. Chem. Rev.  2008,  108:  2887 
    Google Scholar
  • 2c Álvarez-Corral M. Muñoz-Dorado M. Rodríguez-García I. Chem. Rev.  2008,  108:  3174 
    Google Scholar
  • 2d Naodovic M. Yamamoto H. Chem. Rev.  2008,  108:  3132 
    Google Scholar
  • 2e Nájera C. Sansano JM. Yus M. J. Braz. Chem. Soc.  2010,  21:  377 
    Google Scholar
  • 2f Kissane M. Maguire AR. Chem. Soc. Rev.  2010,  39:  845 
    Google Scholar
  • 3a Nájera C. Sansano JM. Org. Biomol. Chem.  2009,  7:  4567 
    Google Scholar
  • 3b Nájera C. Sansano JM. Monatsh. Chem.  2011,  142:  659 
    Google Scholar
  • 4a Ma D. Yang J. J. Am. Chem. Soc.  2001,  123:  9706 
    Google Scholar
  • 4b Hughes CC. Trauner D. Angew. Chem. Int. Ed.  2002,  41:  4556 
    Google Scholar
  • 4c Kleinsasser NH. Wallner BC. Harreus UA. Zwickenpflug W. Richter E. Toxicology  2003,  192:  171 
    Google Scholar
  • 4d Stapon A. Li R. Townsend CA. J. Am. Chem. Soc.  2003,  125:  8486 
    Google Scholar
  • 5 Fisk JS. Mosey RA. Tepe JJ. Chem. Soc. Rev.  2007,  36:  1432 
    CrossrefPubMedGoogle Scholar
  • 6a Karoyan P. Sagan S. Lequin O. Quancard J. Lavielle S. Chassaing G. Targets Heterocycl. Syst.  2004,  8:  216 
    Google Scholar
  • 6b Nájera C. Sansano JM. Chem. Rev.  2007,  107:  4586 
    Google Scholar
  • 6c Calaza MI. Cativiela C. Eur. J. Org. Chem.  2008,  3427 
    Google Scholar
  • 6d Asymmetric Synthesis and Applications of α-Amino Acids   Soloshonok VA. Izawa K. American Chemical Society; Washington DC: 2009. 
    Google Scholar
  • 7 Alba A.-NR. Ríos R. Chem. Asian J.  2011,  6:  720 
    CrossrefPubMedGoogle Scholar
  • 8 Peddibhothla S. Tepe JJ. J. Am. Chem. Soc.  2004,  126:  12776 
    CrossrefGoogle Scholar
  • 9a Melhado AD. Luparia M. Toste FD. J. Am. Chem. Soc.  2007,  129:  12638 
    Google Scholar
  • 9b Melhado AD. Amarante GW. Wang J. Luparia M. Toste FD. J. Am. Chem. Soc.  2011,  133:  3517 
    Google Scholar
  • 10a Martín-Rodríguez M. Nájera C. Sansano JM. Wu FL. Tetrahedron: Asymmetry  2010,  21:  1184 ; corrigendum: Tetrahedron: Asymmetry 2010, 21, 2559
    Google Scholar
  • 10b

    Martín-Rodríguez, M.; Nájera, C.; Sansano, J. M.; de Cózar, A.; Cossío, F. P. submitted for publication

  • 10c Martín-Rodríguez M. Nájera C. Sansano JM. de Cózar A. Cossío FP. Beilstein J. Org. Chem.  2011,  7:  988 
    Google Scholar
  • For recent reviews, including recent examples of the use of [(AuX)2(P-P)*] complexes in catalysis, see:
  • 11a Hashmi ASK. Chem. Rev.  2007,  107:  3180 
    Google Scholar
  • 11b Wiedenhoefer RA. Chem. Eur. J.  2008,  14:  5382 
    Google Scholar
  • 11c Gorin DJ. Sherry BD. Toste FD. Chem. Rev.  2008,  108:  3351 
    Google Scholar
  • 11d Sengupta S. Shi X. ChemCatChem  2010,  2:  609 
    Google Scholar
  • 12 Wheaton CA. Jennings MC. Puddephatt RJ. Z. Naturforsch., B  2009,  64:  1469 
    Google Scholar
13

For the typical procedure and data of the isolated products, see Supporting Information.