A Double Deprotonation Strategy for Cascade Annulations of Palladium–Trimethylenemethanes and Morita–Baylis–Hillman Carbonates to Construct Bicyclo[3.1.0]hexane Frameworks

Abstract Here we report that the chemoselective activation of Tsuji's 2‐(cyanomethyl)allyl carbonates to generate the palladium–trimethylenemethane 1,3‐dipoles via a deprotonation strategy can be realized in the presence of Morita–Baylis–Hillman carbonates from substantial activated ketones. The following S N 2′‐addition enables the formation of new 1,3‐dipole species having an activated alkene moiety through a second deprotonation process, which then undergo cascade [1+2]/[3+2] annulations to furnish complex bicyclic [3.1.0]hexane frameworks having three contiguous quaternary stereogenic centers with good to excellent enantioselectivity. Moreover, by using benzoyl aldehyde‐derived substrates, a [1+4]/[3+2] annulation sequence is similarly developed to produce fused cyclopenta[b]furan architectures.