Facile Synthesis of Allylic Nitro Compounds by N,N-dimethylethylenediamine-Catalyzed Condensation of Aliphatic and Alicyclic Ketones with Primary Nitroalkanes

Article abstract of DOI:10.1021/jo00373a007

Aliphatic as well as alicyclic ketones condense with primary nitroalkanes in the presence of N,N-dimethylethylenediamine (1) to give allylic nitro compounds selectively in good to excellent yields without forming α-nitro olefins.Condensation of 2-alkanones and 2-methylcyclopentanone with nitromethane produces the products of thermodynamic control, while the product of kinetic control is obtained from 2-methylcyclohexanone.Propiophenone, an aromatic ketone, reacted with nitromethane in a way analogous to aliphatic ketones to give the corresponding allylic nitro product.A reaction mechanism to account for the exclusive formation of allylic nitro compounds is proposed.Some allylic nitro compounds thus obtained are converted into α,β-unsaturated aldehydes and ketones by treatment with sodium methoxide and then TiCl3 in buffered solution.