The applications of free radical intermediates in organic synthesis have expanded significantly in recent years. However, catalytic strategies that enable control of enantioselectivity in radical reactions remain rare. In this lecture, I will describe three recent projects that all make use of attractive non-covalent associations between free radicals (or radical ions) and chiral catalysts as a basis for stereocontrol. Mechanistic and computational efforts to elucidate the precise radical-molecule interactions responsible for asymmetric induction will be presented.


Robert Knowles (Princeton University)