A. Forging quaternary centers via sp 2 -sp 3 coupling Indeed, none of the compounds in Figure can be accessed with such logic as one is generally restricted to heteroarenes that can be easily constructed from carbonyl or alkyne appendages, leading to a non-modular strategy. Aside from the bespoke methods outlined above, crosscouplings to access such structures must be evaluated on a case-by-case basis. For example, Shenvi's powerful hydroarylation approach can ac-cess certain scaffolds such as If the alkyl bromide is available, Sevov and Gong's cross-electrophile couplings are potentially useful options for compounds such as If the alkyl amine is available, deaminative cross couplings might be of use for compounds such as Finally, if an ester is desired at the quaternary carbon, Hartwig's small-ring arylation disclosure could be very effective (23). The BINAP/Py-enabled Ni-electrocatalytic conditions described in Table were applied across a range of arenes and redox active esters to access all of the structures outlined in Figure . In order to place these results in the proper context, comparisons to the original Ag/Ni conditions are shown in addition to recent photochemical conditions that were optimized for hindered couplings (9 out of 52 arylations in that study formed quaternary centers with the remainder being fully substituted centers with an adjacent heteroatom), and other chemical and photochemical methods.