Transition-Metal-Free Silylation of Unactivated C(sp²)–H Bonds with <i>tert</i>-Butyl-Substituted Silyldiazenes

Aromatic organosilanes bearing C(sp2)–Si bonds have found increasing applications across the chemical science, yet are mostly produced by atom-uneconomical stoichiometric procedures. Catalytic alternatives using hydrosilanes as silicon sources also been described, but they display unfavorable thermodynamics and based on expensive catalytic systems, often derived from noble metals, or lack generality. Herein, we describe use of an alternative source, namely tert-butyl-substituted silyldiazenes (tBu–N═N–SiR3), that readily accessible commercially available precursors whose structure enables C(sp2)–H bond silylation unactivated heteroaryl aryl compounds under ambient, transition-metal-free conditions.