After identifying the optimal reaction conditions for conducting the hydro-semipinacol rearrangement of 1a enantioselectively we evaluated these conditions with a series of symmetric α,α-diarylallylic alcohols (Scheme 1). The simplest substrate 1b with unsubstituted arenes delivered product (R)-2b in 96% yield and 99 : 1 er. The absolute (R)-configuration within ketone 2b was determined by comparing its specific rotation to a literature value, and the remaining product configurations have been assigned by analogy. A range of alkyl substituents in the para-position, some bearing benzylic hydrogens, and a 4-phenyl analogue all gave comparable results with products, (R)-2c-2f, obtained in 70-90% yield with high levels of enantioenrichment. The reaction accommodated the presence of bromine (2g) or chlorine (2h) atoms and provides a synthetic handle for further manipulations. Highly electron-donating substrates were less well tolerated, affording a lower yield of 31% for the p-methoxy product (R)-2i with significant formation of a 4,4'-dimethoxybenzophenone byproduct. Despite attempts to thoroughly purge the reaction vessel with inert gas we could not overcome this deleterious side reaction; nevertheless, high levels of enantioselectivity were maintained. Tempering the electron density of the substrate by using a phenyl ether (2j) restored the yields to synthetically useful levels. A thioether (2k) and TMS-protected alkyne (2l) were compatible under the oxidative reaction conditions with the products having 98 : 2 er and 95 : 5 er, respectively. An evident drop in enantioselectivity was noted by introducing the strongly electron-withdrawing trifluoromethyl group either at the para-(2m) or meta-(2n) position of the aromatic ring. Although, at least for example 2m demonstrates the alkylcobalt(IV) intermediate is sufficiently electrophilic to promote 1,2-migration of a severely electron-deficient arene. Relatively less electron-deficient derivatives, such as m-chloro (2o) or m-fluoro (2p) substituents, were better tolerated and gave the corresponding α-arylated ketones with high levels of enantiopurity. The presence of an ortho-substituent did not drastically hamper reactivity, but it did significantly affect the enantioselectivity. For example, o-chloro (2q) or o-methyl (2r) groups returned the products in good yield (70-80%) but as racemic mixtures. Even a small perturbation at this site had a substantial impact as the o-fluoro product (2t) was obtained in 65 : 35 er, which is a notable difference when compared to the paraand meta-analogues (2a and 2p, respectively). We postulate that the presence of an ortho-group might encourage the reaction to proceed via a free carbocation or radical intermediate, facilitated by the heterolytic or homolytic cleavage of the cobalt-carbon bond. The asymmetric 1,2-migration process was also amenable to heteroaromatic rings with benzofuran (2u), benzothiophene (2v), and thiophene (2w) all giving commendable levels of enantioenrichment. Lastly, an electron-rich naphthyl ring system worked well to afford product (R)-2x in 85% yield and in 97 : 3 er.