Direct Remote Asymmetric Bisvinylogous 1,4-Additions of Cyclic 2,5-Dienones to Nitroalkenes

Here we report that cyclic 2,5-dienones can act as bisvinylogous precursors through in situ generation of linear trienamine species with a cinchona-derived primary amine, and exclusively remote ε-regioselective 1,4-additions to nitroalkenes were accomplished in moderate to high enantioselectivity. Moreover, a diversity of complex spirocyclic frameworks could be efficiently constructed in an enantioenriched manner from these multifunctional 1,4-adducts via subsequent vinylogous iminium and even cascade iminium catalysis of the same amine.