LEWIS ACID-CATALYZED CHEMOSELECTIVITY CONTROLLED N-ALKYLATION AND C-ALKYLATION OF ANILINES USING VINYL ARENES

The reaction environment is a powerful lever for steering chemoselectivity. Here, we show that Lewis acid identity can switch couplings of anilines and vinyl arenes between C-alkylation (hydroarylation) and N-alkylation (hydroamination) under metal-free conditions. By tuning the Lewis acid, solvent, temperature, and stoichiometry, either product manifold can be delivered on demand. A broad survey of substrates reveals predictable trends aligned with benzylic stabilization and aniline electronics, enabling practical access to pharmaceutically-relevant scaffolds. Collectively, these results establish a switchable chemoselectivity model for aniline-alkene functionalization and highlight reaction-environment engineering as a general strategy for method development and late-stage diversification.