The pursuit of a reliable means to access the 2-amino-1-arylethanol unit in high enantiopurity via modular cross-coupling was built off of prior studies from this lab; specifically, the recently disclosed electrochemical decarboxylative alkenylation/arylation uniquely promoted by Agnanoparticles (AgNP). Since Csp 2 -Csp 3 bonds are ubiquitous across natural products and pharmacophores, this transformation is highly useful for rapid and modular construction of carbon skeletons from readily available carboxylic acids and alkynyl/aryl halides. The feasibility of controlling the stereochemistry in this radical-based cross-coupling was supported by the recent disclosure of 2 nd -generation doubly decarboxylative coupling, where careful selection of building block structures as well as reaction conditions rendered alkyl-alkyl bond formation highly diastereoselective. Notably, Ley auxiliary-based RAE 6 (Figure ) was used for the highly stereoselective synthesis of ent-SF2768 and complanine, which set the stage for our exploration in the context of diastereoselective arylation. Initial forays were directed at identifying an inexpensive aminoalcohol "cassette" that could lead to high dr and conversion. Numerous constructs based on Ley's auxiliary were evaluated such as 6-9 in the cross coupling with aryl iodide 5. Unfortunately, the observed dr (6 and 7) or yield (8) was too low, or the requisite RAE could not be easily prepared (9). Extensive ligand screening to improve the diastereoselectivity was fruitless, although ligand structures seemed to modestly affect diastereoselectivity (see SI for detail). The promising leads emerged when exploring Seebach-oxazolidines such as 10 wherein high dr was observed albeit in low yield. Changing the nitrogen protecting group to Boc (11) maintained high diastereoselectivity, confirming a robust stereochemical control regardless of the steric bulk of the protecting group. Based on this observation, extensive optimization was conducted as outlined in Figure between RAE 10 and aryl iodide 12. The latter was chosen for an eventual application to the synthesis of GSK-656 (4, Figure ). The organometallic and electrochemical parameters were thus explored in a systematic fashion (for a more comprehensive summary, see SI). For instance, the use of simple bipyridine (bpy) as ligand resulted in the highest yield of all ligands screened (entry 1). The absence of ligand or the use of tridentate ligands such as terpyridine shut down the reaction (entry 3). Reducing the current from 12 mA to 4 mA doubled the observed yield (entry 4). A further improvement was observed after solvent screening with DMA emerging as the best (entry 5-6).