Notwithstanding innumerable advances in asymmetric synthesis, access to enantiopure dialkyl carbinols remains a formidable challenge in organic synthesis. This is especially the case with substrates bearing near identical alkyl sidechains from the standpoint of sterics and electronics (Figure ). Thus, the most intuitive pathways such as kinetic resolution, 1 asymmetric reduction, and nucleophilic addition to aldehydes are of little use in such contexts. Historically, polar bond disconnections have been employed to successfully access such molecules. For example, the nucleophilic opening of epoxides leverages the robust existing methods to access enantiopure epoxides such as Jacobsen HKR and Sharpless AE 5 (strategy A). Asymmetric reduction of ketones is also viable when unsaturation on one side of the carbonyl compound is present such as enones and ynones (strategy B). Although such strategies can enable access to challenging enantiopure alcohols of this type, multistep sequences are needed to access and manipulate the requisite building blocks. This conundrum is illustrated with the case study shown in Figure . Carbinol 1, a key intermediate for the synthesis of Cryptorigidifoliols K and E, has been previously accessed through strategies A and B in 8 and 11 steps respectively. In the former case, only two of the 8 steps forge C-C bonds. Chirality is derived from a Jacobsen HKR (epoxide 3, 46% yield, 99% ee) and roughly half of the synthesis involves functional group manipulations. In the latter approach, an ynone 5 is targeted and reduced using CBS (87% yield, 98% ee). Only three of 11 steps make a C-C bond, leaving 7 additional concession steps (FG, PG, and non-strategic redox manipulations). Radical retrosynthesis 9 applied to the same molecule could in principle lead to a far more direct approach, wherein a racemic a-hydroxy acid and an organometallic reagent are combined in an enantioselective decarboxylative coupling. This case study, and many others like it, inspired the pursuit of such a method. In this Article the development of such a transformation is described (Figure ). Enlisting redox-active esters and organozinc nucleophiles in the presence of a Ni-catalyst and carefully selected chiral ligand, broad access to challenging dialkyl carbinols is exemplified along with numerous applications demonstrating its ability to simplify synthesis. The use of radical methods to access dialkyl carbinols is not a novel idea. In fact, its origins can be traced back to the mechanistic studies of the Barbier reaction suggesting a single electron process rather than an anionic pathway. Excluding that large class of reactions, the historical picture can be summarized succinctly as shown in Figure with three general strategies often being employed using aldehyde precursors as either radical precursors or acceptors, and many other a-oxy alkyl radical precursors. In 1986, it was shown that ketyl radicals could be generated from aldehydes using SmI2 and subsequently coupled to olefins. 11 Several variations of this theme have subsequently been reported using different metals, 12 photoinduced electron transfer, or even electrochemistry. More recently, the Montgomery group has leveraged the power of Ni-catalysis to access silyl-protected products using either alkyl bromides or redox-active esters (RAEs). Taking advantage of the electrophilic properties of aldehydes it has also been shown that nucleophilic radicals can smoothly react in both intra-and intermolecular modes. In the former case, canonical Ti- and Sn-based 17 radical initiation conditions were employed using epoxides and alkyl iodides, respectively. In the latter case, it was recently demonstrated that Fe-H based HAT reactivity on olefins is compatible with aldehyde electrophiles to generate branched dialkyl carbinol products. Finally, numerous a-oxy alkyl radical precursors have been employed to achieve C-C bond formation. Thus, the use of O-heteroatom acetals containing S, 19 Se 20 and halogen atoms have been employed in intermolecular couplings with olefins. The decarboxylative Negishi alkylation of a-oxo RAEs was also reported. When a prexisting stereocenter is adjacent to the reaction site high dr was observed.