Enantioselective benzylic functionalization methods use the complexed chromium tri(carbonyl) moiety essentially as a chiral auxiliary. Approach of the functionalizing reagent anti to the ----chromium tri(carbonyl) fragment leads to a single diastereomer of the product complex. After removal of the chromium group with light or an oxidizing agent such as iodine, a nearly enantiopure product remains. See the Scope and Limitations section below for several methods for diastereoselective benzylic functionalization.