Deacylative allylation of nitroalkanes: unsymmetric bisallylation via 3-component coupling

Catalytic Tsuji-Trost allylation has become a ubiquitous method for allylation of active methylene compounds.[1] While monoallylation products are typically formed, bisallylation of malonates and related ketone enolates leads to 1,6-dienes.[2] Given the utility of these 1,6heptadienes in metal-catalyzed cycloisomerization reactions,[3] it would be beneficial if one could perform controlled bisallylation of less stabilized carbon nucleophiles. Unfortunatly, the one-pot bisallylation of other carbon nucleophiles is not well documented and usually requires harsh reaction conditions.[4] Moreover, the addition of two different allyl electrophiles to form unsymmetric 1,6-dienes in a one-pot operation is exceedingly rare.[5] Herein, we describe the development of an unsymmetric bisallylation of carbon nucleophiles and introduce catalytic deacylative allylation as a new strategy for tandem in situ generation and coupling of nucleophiles with allyl electrophiles (eq. 1).1