A Precise SyntheticToolbox: H‑Bond-AssistedQuadruple Reactivity of <i>o</i>‑Dimethylaminoaryloximes

Non-covalent interactions are a highly promising tool for the development of transition-metal-free chemospecific synthetic transformations. Here, we demonstrate the implementation of non-covalent interactions as a simple, precise, and flexible synthetic toolbox, allowing the controlled transformation of <i>o</i>-dimethylaminoaryloximes into nitriles and hard-to-reach nitrogen heterocycles under mild conditions. This diverse reactivity is activated via hydrogen bonding and facilitated via the “buttressing effect” of the substituents next to the NMe₂ group. All transformations require only simple and easily available acids and solvents, which generally provide precise control over the direction of the reaction, allowing the selective synthesis of nitriles, fused pyrazoles, isoxazoles, and pyrroles.