This work adds to the small but growing number of asymmetric mHAT reactions enabled by small-molecule catalysts, and provides, to the best of our knowledge, the first demonstration of asymmetric hydrogenation via iron-catalyzed mHAT. Further, it shows the potential for cooperative reactivity between iron and thiols. The compatibility of chiral thiol catalysts with these Fe-catalyzed reactions creates an exciting opportunity for the development of novel asymmetric iron-catalyzed mHAT reactions.