The reaction between tricarbonylchromium complexes Cr(CO)L and electron-rich or electron-neutral aromatic rings produces tricarbonyl(arene)chromium complexes (arene)Cr(CO). Complexation to chromium(0) activates the side chain of the arene, facilitating dissociation of a benzylic proton, leaving group, or nucleophilic addition to the homobenzylic position of styrenes. Further transformations of the resulting conformationally restricted, benzylic anion or cation involve the approach of reagents exo to the chromium fragment. Thus, benzylic functionalization reactions of planar chiral chromium arene complexes are highly diastereoselective. Additionally, the chromium tri(carbonyl) fragment can be used as a blocking element in addition reactions to ortho-substituted aromatic aldehydes and alkenes. An ortho substituent is necessary in these reactions to restrict conformations available to the aldehyde or alkene. Removal of the chromium fragment to afford the metal-free functionalized aromatic compound is possible photolytically or with an oxidant.