Historical Background. Asymmetric hydrogenation of olefins is among the most widely used transformations to prepare chiral molecules from prochiral substrates, 1 with classic methods for transition metal-catalyzed asymmetric hydrogenation based on the oxidative addition of H2 (Scheme 1a). While these reactions are high performing and widely used, they historically require substrates with coordinating functional groups for chelating, two-point metal binding to facilitate enantioinduction 3 with limited exceptions. Further, the highest enantioselectivity is observed with electron-poor olefins ("activated olefins"), as interactions between the substrate and the metal are best promoted by substituents on the olefin that are typically electron-withdrawing. Recently, hydrogenation of electronneutral, electron-rich ("unactivated"), and minimally functionalized olefins has seen growing improvement and success; however, lower enantioselectivity is commonly observed, and fewer methods are available. In this context, radical hydrofunctionalization enabled by metalcatalyzed hydrogen atom transfer (mHAT, Scheme 1b) reactions have particular promise as they do not require metal coordination of the olefin for reactivity. Mechanistically, mHAT involves a metalhydride intermediate that transfers H• to the olefin to generate an alkyl radical that may be trapped under mild conditions. mHAT chemistry has been used for olefin hydrofunctionalizations 8 with inexpensive Fe, Co, and Mn catalysts and exhibits excellent functional group tolerance, permitting late-stage functionalizations in total synthesis. 9