Palladium‐Catalyzed Tandem Cycloisomerization/Cross‐Coupling of Carbonyl‐ and Imine‐Tethered Alkylidenecyclopropanes

Pd(0) catalysts featuring phosphorus‐based monodentate ligands can detour the reactivity of carbonyl‐tethered alkylidenecyclopropanes (ACPs) from standard (3+2) cycloadditions towards tandem cycloisomerization/cross‐coupling processes. This new reactivity lies on the formation of key π‐allyl oxapalladacyclic intermediates, which are subsequently trapped with external nucleophilic partners, instead of undergoing canonical C−O reductive eliminations. Importantly, the use of imine‐tethered ACP's is also feasible. Therefore, the method provides a straightforward and stereoselective entry to a wide variety of highly functionalized cyclic alcohols and amines.