Asymmetric hydrogenation– the addition of hydrogen across a substrate’s carbon-carbon double bond, as mediated by transition metal catalysts– is an atom-economical process used to synthesize chiral active pharmaceutical ingredients (APIs). Though precious metal (such as rhodium) hydrogenation catalysts are well-studied, they have significant fluctuations in price and large global warming potential values as compared to earth-abundant metals (such as cobalt). The Chirik Group has developed active and selective Co(0) and Co(I) precatalysts containing bis(phosphine) ligands. This work examines the functional tolerance of cationic Co(I) and neutral Co(0) precatalysts using two model substrate classes: indazole-containing enamides (precursors to Zavegepant, an API used to treat migraines) and dehydroamino acids (precursors to L-DOPA, an API used to treat Parkinson’s disease). High-pressure asymmetric hydrogenation reactions resulted in the active and selective hydrogenation of indazole-containing enamides, as revealed by nuclear magnetic resonance (NMR) spectroscopy and chiral supercritical fluid chromatography analysis. Full conversion to product was observed in the asymmetric hydrogenation of dehydroamino acids with BenzP* cationic Co(I) and neutral Co(0) precatalysts, representing a direct Co-catalyzed route to L-DOPA precursors. In-situ studies monitored by 1H and 31P NMR spectroscopy investigated precatalyst stability and precatalyst-substrate interactions in methanol, providing preliminary insight into precatalyst activation– the conversion of well-defined cation to an unidentified phosphorus-containing species was observed at room temperature. Overall, this work shows the tolerance of cationic bis(phosphine) Co(I) and neutral bis(phosphine) Co(0) precatalysts in the asymmetric hydrogenation of enamides containing indazole and carboxylic acid functionalities.