Relaxation to the ground-state via back-electron transfer would ultimately regenerate the cyclopropane in the confines of a chiral environment. Accordingly, enantioselectivity would be encoded at the single chiral photocatalyst level. To validate the hypothesis described in Figure , the catalytic deracemization of cyclopropane rac-1 was investigated using the commercial aluminum salen complex Al-1 in acetone (Fig. ) at -70 °C. Guided by the absorption spectra of photocatalyst and substrate (Fig. ), selective catalyst excitation was achieved by irradiation of the reaction mixture at 400 nm (3 W LED). After 4.5 h, enantioenriched product 1 was isolated in 78% yield (e.r. 87:13). Encouraged by this result, a process of reaction optimization was initiated (Fig. , for full optimization table see Supporting Information), beginning with the addition of a soluble salt to stabilize the charge-separated intermediates. The addition of n-Bu4NCl enhanced both the yield (80%) and enantioselectivity (e.r. 90:10, entry 1). 51 Absorption Rigorous exclusion of oxygen also proved to be essential in achieving efficient deracemization.