Study based on electronic descriptors of the diastereoselective aza-diels-alder cycloaddition of [(1r)-10-(n,n-diethylsulfamoyl)isobornyl] 2h-azirine-3-carboxylate to e,e-1,4-diacetoxy-1,3-butadiene

• YASSER B RUIZ-BLANCO ^[4] ; MARIA J ALVES ^[1] ; JOSÉ E RODRÍGUEZ-BORGES ^[2] ; REINALDO MOLINA ^[3]
  1. [1] Universidade do Minho

     Universidade do Minho

     Braga (São José de São Lázaro), Portugal

     
  2. [2] Universidade Do Porto

     Universidade Do Porto

     Santo Ildefonso, Portugal

     
  3. [3] Universidad Central de Las Villas

     Universidad Central de Las Villas

     Cuba

     
  4. [4] Universidad Central. Marta Abreu de las Villas Facultad de Química y Farmacia Unit of Computer-Aided Molecular Biosilico Discovery and Bioinformatic Research

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• Localización: Journal of the Chilean Chemical Society (Boletín de la Sociedad Chilena de Química), ISSN-e 0717-6309, ISSN 0366-1644, Vol. 58, Nº. 4, 2013, págs. 2243-2247
• Idioma: inglés
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• Resumen

  • Cycloaddition of chiral [(1R)-10-(N,N-diethylsulfamoyl)isobornyl] 2H-azirine-3-carboxylate to E,E-1,4-diacetoxy-1,3-butadiene shows complete diatereoselectivity giving a single cycloadduct (-)-(2S,5R,6R)-6-[(1R)-10-(N,N-diethylsulfamoyl)isobornyloxycarbonyl]-1-azabicyclo[4.1.0]hept-3-ene-2,5-diyldiacetate. Our main objective is to identify electronic/steric parameters capable of describing the observed tendencies of this reaction. The results of the calculations conclude that: even though the steric factors can play an important role at the initial steps of the reaction, at the transition states the behavior of several electronic parameters; like hardness, polarizability, aromaticity, charge transfer, etc is decisive enough to justify the obtained product. Finally, this work summarizes an exhaustive analysis of electronic descriptors and empirical reactivity principles, reaching a definitive and comprehensive explanation to the observed experimental result.