In summary, an enantioselective alkyl e-NHK has been developed. This reaction allows the addition of simple, primary alkyl substrates to aldehydes to give secondary alcohols in high enantioselectivity. This class of substrates has not previously been rendered enantioselective for NHK reactions driven by canonical metal dust reductants. This asymmetric alkyl e-NHK was enabled by using TDAE as a key reductive mediator. CV studies and stoichiometric experiments suggest that the role of TDAE is to mediate reduction of the L7•Cr III complex, which in the previous, nonasymmetric alkyl e-NHK, was found to be the rate determining step. This is especially beneficial for the asymmetric reaction, in which the chiral ligand is proposed to kinetically slow reduction of the catalyst at the electrode. The ability to use catalytic TDAE mediator is critical to avoid competing HAT processes between the alkyl radical and TDAE +• . The usefulness of this method is demonstrated by multiple synthetic campaigns, which highlight the strategic deployment of the asymmetric alkyl e-NHK to increase synthetic ideality and reduce step count.