Abstract
In the past years, Pd(0) -catalyzed C(sp(3) )-H activation provided efficient and step-economical methods to synthesize carbo- and heterocycles via direct C(sp(2) )-C(sp(3) ) bond formation. We report herein that a 1,4-Pd shift allows access to N-heterocycles which are difficult to build via a direct reaction. It is shown that o-bromo-N-methylanilines undergo a 1,4-Pd shift at the N-methyl group, followed by intramolecular trapping by C(sp(2) )-H or C(sp(3) )-H activation at another nitrogen substituent and remote C-C bond formation to generate biologically relevant isoindolines and β-lactams. The product selectivity is influenced by the employed ligand, with NHCs favoring the product of remote C-C coupling against products arising from direct C-C coupling and N-demethylation.