With the basic reactivity problem being solved, attention turned to the second obstacle: achieving diastereoselective coupling. In principle, 6 could serve as a versatile "cassette" that could be easily employed to make a vast array of polyketide natural products. Based on the assumption that the ligand could affect stereochemical outcome, those that were previously found to be effective for dDCC were re-screened. This extensive screen led to the discovery that terpyridine together with MgCl2 as Lewis acidic additive rendered the coupling highly diastereoselective, favoring the cis-diol product (6R)-12 (>20:1 dr). In striking contrast, the omission of ligand under these modified conditions still led to successful coupling, yet the diastereoselectivity was completely reversed to deliver trans-diol product (6S)-12 (>20:1 dr, see SI for working hypothesis). Additional experiments were conducted to determine if such a unique stereochemical outcome could be translated into other analogous reaction manifolds. However, attempts to replicate this coupling under photochemical and metal-powder conditions were unsuccessful. The unique electrochemically enabled reactivity observed may stem from the fact that dDCC requires multiple concurrent reduction events: simultaneous reduction of two different RAEs along with reduction of Ni catalyst. Maintaining the subtle balance of these multiple reduction events may be a demanding task for alternative reductants.