The effects of aryl ring ortho-, meta-, and para-substitution on site selectivity and enantioselectivity were investigated in the following reactions: (1) enantioselective Pd-catalyzed redox-relay Heck reaction of arylboronic acids, (2) Pd-catalyzed β-aryl elimination of triarylmethanols, and (3) benzoylformate decarboxylase-catalyzed enantioselective benzoin condensation of benzaldehydes. Through these studies, it is demonstrated that the electronic and steric effects of various substituents on selectivities obtained in these reactions can be described by NBO charges, the IR carbonyl stretching frequency, and Sterimol values of various substituted benzoic acids. An extended compilation of NBO charges and IR carbonyl stretching frequencies of various substituted benzoic acids was used as an alternative to Hammett values. These parameters provide a correlative tool that allows for the analysis of a much greater range of substituent effects because they can also account for proximal and remote steric effects.