Synthesis of Quaternary and Tertiary Carbon‐Substituted Arenes by Lewis Base Promoted Site‐Selective Coupling with Allylic Nucleophiles

Abstract A practical method for the preparation of quaternary and tertiary allyl‐substituted heteroarenes by site‐selective couplings of heteroaryl nitriles and allylic nucleophiles is disclosed. Transformations utilize readily accessible stable reagents, proceed in the presence of a Lewis base activator, and undergo aryl‐C(sp 3 ) quaternary and tertiary carbon formation with high γ‐selectivity (up to >98 : 2 γ : α).