PdCl2-catalyzed efficient allylation and benzylation of heteroarenes under ligand, base/acid, and additive-free conditions.

We present a PdCl(2)-catalyzed protocol for highly efficient allylation and benzylation of a rich variety of N-, O-, and S-containing heteroarenes under base/acid, additive, and ligand-free conditions. The method represents the very few examples for simple, universally applicable, clean, and atom-efficient functionalization of heteroarenes.