Memory of Chirality in Radical Addition–Translocation–Cyclization Cascades

ABSTRACT The memory of chirality (MoC) in radical addition‐translocation‐cyclization (RATC) cascades involving chiral nonracemic alkynes has been examined using different hydrofunctionalization procedures. A high level of retention of configuration could be achieved when the rate of cyclization was enhanced due to favorable polar effects. The best system discovered so far was the use of the very electrodeficient pentafluorobenzenesulfonyl moiety. The MoC observed is remarkable if one considers that the system examined possesses no conformational constrain since only σ‐bonds are present in the backbone.