Palladium-Catalyzed Aminomethylation of Nitrodienes and Dienones via Double C-N Bond Activation

Main observation and conclusion A new strategy for the generation of the active Pd-alkyl species from aminal via C-N bond activation has been established,in which the formation of zwitterionic intermediate through aza-Michael addition of aminal to nitrodienes or dienones is identified as a key step for the activation of the C-N bond.The efficient strategy has enabled a new palladium-catalyzed a-aminomethylation of nitro-dienes and dienones via double C-N bond activation.The scope and versatility of the reaction were demonstrated and a broad range of substrates bearing electron-donating and-withdrawing groups on the aromatic rings were all compatible with this reaction to furnish the desired a-aminomethylated products in moderate to good yields with excellent regioselectivities and E/Z selectivities.