Artículos de revistas
A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources
Fecha
2015-08Registro en:
Gerosa, Gabriela Guillermina; Spanevello, Rolando Angel; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; A joint experimental, in silico and NMR studies towards the rational design of iminium-based organocatalyst derived from renewable sources; American Chemical Society; Journal Of Organic Chemistry; 80; 15; 8-2015; 7626-7634
0022-3263
Autor
Gerosa, Gabriela Guillermina
Spanevello, Rolando Angel
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
Resumen
An efficient organocatalyst for iminium-ionbased asymmetric Diels−Alder (DA) reactions has beenrationally designed. The most influential structure−activityrelationships were determined experimentally, while DFTcalculations and NMR studies provided further mechanisticinsight. This knowledge guided an in silico screening of 62different catalysts using an ONIOM(B3LYP/6-31G*:AM1)transition-state modeling, which showed good correlationbetween theory and experiment. The top-scored compoundwas easily synthesized from levoglucosenone, a biomass-derived chiral enone, and evaluated in the DA reaction between (E)-cinnamaldehyde and cyclopentadiene. In line with the computational finding, excellent results (up to 97% ee) were obtained. Inaddition, the catalyst could be easily recovered and reused with no loss in its catalytic activity.