Predictive control over the selectivity outcome of an organic synthetic
method is an essential hallmark of reaction success. Electricity-driven
synthesis offers a reemerging approach to facilitate the design of
reaction sequences towards increased molecular complexity. In addition
to the desirable sustainability features of electroorganic processes,
the inherent interfacial nature of electrochemical systems present
unique opportunities to tune reaction selectivity. To illustrate this
feature, we outline examples of mechanism-guided interfacial control
over CO2 electroreduction selectivity, a well-studied and instructive
electrochemical process with multiple reduction products that are
thermodynamically accessible. These studies reveal how controlled proton
delivery to the electrode surface and substrate electroadsorption with
the electrode dictate reaction selectivity. We describe and compare
simple, yet salient, examples from the electroorganic literature, where
we postulate that similar effects predominate the observed reactivity.
This perspective highlights how the interface serves as a tunable
dimension in electrochemical processes, delineating unique tools to
study, manipulate, and achieve reaction selectivity in
electricity-driven organic synthesis.