Overcoming the limitations of Kolbe coupling with waveform-controlled electrosynthesis.

The Kolbe reaction forms carbon-carbon bonds through electrochemical decarboxylative coupling. Despite more than a century of study, the reaction has seen limited applications owing to extremely poor chemoselectivity and reliance on precious metal electrodes. In this work, we present a simple solution to this long-standing challenge: Switching the potential waveform from classical direct current to rapid alternating polarity renders various functional groups compatible and enables the reaction on sustainable carbon-based electrodes (amorphous carbon). This breakthrough enabled access to valuable molecules that range from useful unnatural amino acids to promising polymer building blocks from readily available carboxylic acids, including biomass-derived acids. Preliminary mechanistic studies implicate the role of waveform in modulating the local pH around the electrodes and the crucial role of acetone as an unconventional reaction solvent for Kolbe reaction.

Lewis acid catalyzed heavy atom tunneling - the case of 1H-bicyclo[3.1.0]-hexa-3,5-dien-2-one.

For many thermal reactions, the effects of catalysis or the influence of solvents on reaction rates can be rationalized by simple transition state models. This is not the case for reactions controlled by quantum tunneling, which do not proceed via transition states, and therefore lack the simple concept of transition state stabilization. 1H-Bicyclo[3.1.0]-hexa-3,5-dien-2-one is a highly strained cyclopropene that rearranges to 4-oxocyclohexa-2,5-dienylidene via heavy-atom tunneling. H2O, CF3I, or BF3 form Lewis acid-base complexes with both reactant and product, and the influence of these intermolecular complexes on the tunneling rates for this rearrangement was studied. The tunneling rate increases by a factor of 11 for the H2O complex, by 23 for the CF3I complex, and is too fast to be measured for the BF3 complex. These observations agree with quantum chemical calculations predicting a decrease in both barrier height and barrier width upon complexation with Lewis acids, resulting in the observed Lewis acid catalysis of the tunneling rearrangement.