Nucleophilic Substitution
Nucleophilic substitution is one of the most fundamentally important class of reactions in organic chemistry. These cost effective and operationally simple reactions are used every day in the discovery and manufacture of new pharmaceuticals, agrochemicals, materials and more. However, there are long-standing limitations typically associated with the classical mechanisms of nucleophilic substitution. We are interested in developing sustainable synthetic methods that can overcome these limitations through catalysis and reagent design.
For example, we have developed a transition-metal-free method for the hydroxylation of aryl halides using oxime anions as hydroxide (–OH) surrogate nucleophiles. These reactions are proposed to proceed via an electron-catalysed radical-nucleophilic substitution (SRN1) chain mechanism. Building on this surrogate approach, we recently developed an easily handled surrogate of the extremely reactive azanide anion (–NH2) for nucleophlic aromatic substitution (SNAr).
See: Chem. Sci. 2021, Chem. Eur. J. 2024
We're also very interested in developing one-step denitrative substitution processes and understanding the mechanisms of these reactions. Most recently, we have developed methods for the denitrative hydroxylation and sulfonylation of nitroarenes.
