Electro-Inductive Effects Control the Yield and Stereoselectivity of Brønsted Acid Catalyzed Reactions

The electro-inductive effect offers a novel approach to modulating the chemical properties of molecules, potentially eliminating the need for laborious synthesis of derivatives with varying functional groups. By transmitting voltage-induced charge polarization from an electrode to molecules covalently attached to its surface, this method mimics the inductive effect of functional groups. Proof-of-principle studies with self-assembled monolayers of thiols on gold electrodes highlighted the transformative potential of this approach to reaction control. However, such demonstrations have so far been limited to single-molecule scales. In this study, we show that the electro-inductive effect can fine-tune the catalytic behavior of arylsulfonic acid immobilized on porous carbon electrodes for Brønsted acid-catalyzed organic reactions at millimolar scales. Applying voltages between –0.9 and +0.8 V relative to the open circuit voltage modulated the yield of acid-catalyzed esterification by a factor of ~3. Furthermore, in the intramolecular nucleophilic substitution of an alcohol bound to a chiral carbon, the stereochemical outcome of the carbocyclization was altered by adjusting the applied voltage. These results establish the electro-inductive effect as a viable alternative to functional group modification for controlling catalytic organic reactions at practically relevant scales.