Ketones as Electrophile in Nitroaldol Reaction: Synthesis of β,β-Disubstituted- 1,3-dinitroalkanes and Allylic Nitro Compounds

• Autor(a) principal: Gomes,Alex O.
• Data de Publicação: 2021
• Outros Autores: Souza,Douglas L. F. de, Costa,Jeronimo S., Pereira,Vera Lúcia P.
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Journal of the Brazilian Chemical Society (Online)
• Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532021000801575
• topic: allylic nitro compounds; DBU; domino reaction; reaction reversible; Michael addition; Henry reaction

Abstract β,β-Disubstituted-1,3-dinitro compounds were obtained exclusively with an overall yield of 83% through a domino nitroaldol/elimination/1,4-addition process, when excess nitromethane was added to cyclohexanone or butanone using DBU (1,8-diazabicyclo[5.4.0]undec-7-ene), as a basic catalyst. On the other hand, β-nitroalcohols could be obtained in 30-84% yield, when nitromethane reacts with different aliphatic ketones in stoichiometric amounts, in the presence of catalytic amounts of K2CO3(s), Amberlyst® -A21 or TBAF.3H2O (tetra-n-butylammonium fluoride trihydrate)/THF (tetrahydrofuran). In addition, a new and versatile route to obtainment of allylic nitro compounds, by treatment of acetylated nitroalcohols and aldehydes in catalytic amounts of DBU or TBAF.3H2O, via a one-pot elimination/nitroaldol reaction sequence, was developed.