Chemoselective synthesis of substituted imines, secondary amines, and beta-amino carbonyl compounds from nitroaromatics through cascade reactions on gold catalysts.

Laura L Santos, Pedro Serna, Avelino Corma

Index: Chemistry 15(33) , 8196-203, (2009)

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Abstract

Substituted imines, alpha,beta-unsaturated imines, substituted secondary amines, and beta-amino carbonyl compounds have been synthesized by means of new cascade reactions with mono- or bifunctional gold-based solid catalysts under mild reaction conditions. The related synthetic route involves the hydrogenation of a nitroaromatic compound in the presence of a second reactant such as an aldehyde, alpha,beta-unsaturated carbonyl compound, or alkyne, which circumvents an ex situ reduction process for producing the aromatic amine. The process is shown to be highly selective towards other competing groups, such as double bonds, carbonyls, halogens, nitriles, or cinnamates, and thereby allows the synthesis of different substituted nitrogenated compounds. For the preparation of imines, substituted anilines are formed and condensed in situ with aldehydes to provide the final product through two tandem reactions. High chemoselectivity is observed, for instance, when double bonds or halides are present within the reactants. In addition, we show that the Au/TiO2 system is also able to catalyze the chemoselective hydrogenation of imines, so that secondary amines can be prepared directly through a three-step cascade reaction by starting from nitroaromatic compounds and aldehydes. On the other hand, Au/TiO2 can also be used as a bifunctional catalyst to obtain substituted beta-amino carbonyl compounds from nitroaromatics and alpha,beta-unsaturated carbonyl compounds. Whereas gold sites promote the in situ formation of anilines, the intrinsic acidity of Ti species on the support surface accelerates the subsequent Michael addition. Finally, two gold-catalyzed reactions, that is, the hydrogenation of nitro groups and a hydroamination, have been coupled to synthesize additional substituted imines from nitroaromatic compounds and alkynes.