The origin of this project stemmed from an analysis of current strategies utilized to synthesize seemingly trivial molecules: chiral dialkyl carbinols. The results of that exercise led to the realization that in the vast majority of cases only two strategies are employed (Figure ), both of which are wedded to two-electron logic (polar bond analysis). Decarboxyaltive Negishi-type alkylation, first disclosed in 2016, can provide a more direct means to access such compounds but in its initial manifestation would only deliver racemic products. This study therefore focused on identifying a suitable ligand and conditions for achieving such a reaction in a general way. To ensure that existing radical-methods did not already solve this problem we carefully benchmarked those pioneering studies to compounds of this type. The developed method exhibits a wide substrate scope with good chemoselectivity and is amenable to gram-scale. It enables more direct and convergent access to structures that were previously prepared through lengthy and laborious routes. Conceptually, this study demonstrates the first highly enantioselective decarboxylative alkylations of readily available racemic a-oxy carboxylates. Its success relies on a simply derived ligand system (three steps from inexpensive phenylglycine methyl ester hydrochloride). More broadly, this study points to the unpredictable nature of ligands with regards to stereocontrol and reactivity in this kind of cross coupling. For example, the L8 which was successfully employed by G.C. Fu to achieve high ee in amino acid-derived couplings furnished only racemic products when NHBoc was replaced with OR. Similarly, the use of L1 for amino acid couplings under our conditions furnished only traces of product.