Completely different reaction outcomes between DC and rAP has thus far been discussed in reductive contexts. Next, the unique effect of rAP in an oxidative manifold will be discussed. The Kolbe reaction is one of the oldest electrochemical reactions and possibly the first C-C bond forming reaction in organic synthesis (Figure ). Despite the appeal of making saturated C-C bonds from simple carboxylic acids by direct oxidation at an electrode, its use in mainstream organic synthesis is exceedingly rare. In its canonical form, a high current density is required to ensure high anodic potential for initiating oxidative radical generation over solvent oxidation, followed by immediate dimerization on a Pt electrode surface (Figure , left). Such harsh oxidative conditions undermine its synthetic utility with even dormant terminal unactivated olefins such as 37 or benzylic systems such as 38 and 39 being incompatible (Figure , right). This severe reaction limitation in addition to the requirement of bulk Pt as electrodes present a major roadblock for practical applications. If such problems could be overcome, the Kolbe reaction could be one of the most atom-economical and powerful Csp 3 -Csp 3 coupling methods known. Such a reaction would be advantageous for large-scale conversion of biomass-derived carboxylic acids into high-value chemicals that are currently supplied from petroleum feedstocks. With these aspirational goals in mind, explorations began with 10-undecenoic acid 37, a seemingly trivial biomassderived acid that is not amenable to Kolbe electrolysis (Figure ). However, its dimerization product (1,19-eicosadiene, 40) could have high utility as a polymer building block (vide infra).