The electrocatalytic asymmetric NHK decarboxylative coupling disclosed herein, when applied strategically, can have a dramatically simplifying impact on synthesis as outlined in Figures and. This is due to the radical retrosynthetic logic employed that departs from the conventional 2e - strategies that are universally employed to access such substrates. For instance, alkyne 54, which previously from 53 (Figure ). Diol 58, an intermediate previously prepared as a racemic mixture (six steps) in a natural product total synthesis, 27 could be prepared in only three steps in high ee (Figure ). The medicinally relevant diol 63 that required an 8-step route could be truncated to only two steps (Figure ). The first total synthesis of horsfieldone A 29 (65) was completed in 2 simple steps from the easily accessed RAE 64 (Figure ). Even more complex applications were designed and implemented as documented in Figure . For example, the herboxidiene analog 70, previously required a 13-step route with many concession steps. In contrast, starting from aldehyde 68 (four steps), an e-NHK coupling followed by cyclization led to the same compound in only 6 total steps. As a testament to the chemoselectivity of this reaction, RAE 69, bearing an electrophilic acrylate moiety could be employed. Finally, a substantially truncated route to gravicycle 31 (78) was developed using a series of enabling electrocatalytic couplings.