Enantioselective Sequential Intramolecular Heck–Matsuda Reaction in the Synthesis of Spirocyclic Heterocycles and Functionalized Furans

The Heck–Matsuda reaction offers significant advantages over conventional Heck processes, as aryldiazonium species readily undergo oxidative addition to Pd(0), enabling transformations under mild conditions. The use of chiral Pd complexes bearing N,N-ligands is an effective strategy to access molecules with stereogenic centers in high enantioselectivity. Furthermore, the in situ generation of diazonium intermediates from anilines avoids the isolation and handling of potentially hazardous diazonium salts, improving both safety and operational simplicity. Moreover, interception of alkyl-Pd intermediates by trapping- reagents enables the introduction of additional functionality, broadening the scope of new molecules.^1,2 Herein, we report an enantioselective sequential intramolecular Heck–Matsuda strategy for the synthesis of spirocyclic heterocycles bearing two stereogenic centers, as well as benzofurans containing terminal olefins, in good yields and with enantiomeric ratios up to 95:5. The method affords a practical methodology to achieve the desired products, enabling efficient access to structurally complex and pharmaceutically relevant architectures.