Expedient and Stereoselective Access to Diverse Alkaloid-like Scaffolds via an Oxidation/Double-Mannich Reaction Sequence

Sequential oxidative cleavage and double-Mannich reactions enable the stereoselective conversion of simple norbornenes into complex alkaloid-like structures. The products undergo a wide range of derivatization reactions, including a regioselec-tive enol triflate formation/cross-coupling sequences and highly efficient conversion to an unusual tricyclic-8,5,5 fused lac-tam. Overall, the process represents a formal 1-atom aza-ring expansion with concomitant bridging annulation, making it of interest for the broader derivatization of alkene feedstocks.