Three-Way Chemoselectivity Switching through Coupled Equilibria

Controlling the chemoselectivity of reactions operating on complex mixtures, including those found in biological and petrochemical feedstocks or in the primordial soup from which life emerged, is generally challenging. The selectivity of imine oxidation can be controlled in dynamic combinatorial libraries, wherein coupled equilibria of imine exchange and the diaza-Cope rearrangement determine whether and when the oxidizable precursor is made available to the oxidant. Adjusting the rate of oxidant addition allows the isolation of three dominant products.