With this new electrochemical cross-coupling platform, elusive C(sp 3 )-C(sp 3 ) linkages were accessed with high relevance to pharmaceuticals and natural products. As an example, this method was amenable to forging vicinal amines and alcohols to form 1,2-substituted alkanes with complete diastereoselectivity through ligand choice, a strategically powerful tool in natural product synthesis. Impressively, the alternate retrosynthetic disconnection enabled by this transformation expedited access to several diverse natural products with a dramatic reduction in overall step count (Figure ). Despite the breadth of chemical space that is accessible with this doubly decarboxylative protocol, the efficient engagement of RAEs derived from tertiary carboxylic acids, and the achievement of an intramolecular variant of this coupling remain elusive. Overcoming the above challenges represents an attractive horizon being explored in our labs.