Allylic amination of unfunctionalized olefins by nitroarenes and CO, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN = bis(phenylimino)acenaphthenequinone) : extension to the synthesis of allylic amines with strongly electron-withdrawing or electron-donating groups on the aryl ring

The allylic amination of unfunctionalyzed olefins by nitroarenes under CO pressure, catalyzed by Ru3(CO)12/Ph-BIAN (Ph-BIAN = bis(phenylimino)acenaphthenequinone) has been extended to some substrates with strongly electron-withdrawing groups on the nitroarene. Reaction of 1,4-dinitrobenzene selectively affords functionalization of only one nitro group, the other remaining unreacted. However, the second nitro group can be reduced in one pot by CO/H2O in the presence of the same catalytic system employed in the amination reaction, to afford the corresponding 4-amino derivative. Some attempts to render the reaction enantioselective by employing chiral bis-oxazolines as ligands in place of Ph-BIAN are described. Bis-oxazolines are suitable ligands for the reaction, although not as efficient as Ph-BIAN, but the allylic amine obtained was found to be racemic.