Ketones as electrophile in nitroaldol reaction: synthesis of β,β-disubstituted1,3-dinitroalkanes and allylic nitro compounds

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 K₂CO_3(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. (author)