Oriented external electric fields (OEEFs) as 'smart reagents' are no longer a theoretical dream. Here, we discuss the wide-ranging potential of using OEEFs to catalyse and control a variety of non-redox reactions and impart selectivity at will. An OEEF along the direction of electron reorganization (the so-called reaction axis) will catalyse nonpolar reactions by orders of magnitude, control regioselectivity and induce spin-state selectivity. Simply flipping the direction of the OEEF or orienting it off of the reaction axis, will control at will the endo/exo ratio in Diels-Alder reactions and steps in enzymatic cycles. This Perspective highlights these outcomes using theoretical results for hydrogen abstraction reactions, epoxidation of double bonds, C-C bond forming reactions, proton transfers and the cycle of the enzyme cytochrome P450, as well as recent experimental data. We postulate that, as experimental techniques mature, chemical syntheses may become an exercise in zapping oriented molecules with OEEFs.
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