Organocatalysis, the use of small organic molecules to catalyze chemical reactions, is of increasing importance in the development of efficient enantioselective reactions. The mechanisms associated with organocatalyzed reactions have received little attention, but are important for the development of more efficient and stereoselective organocatalysts. Current strategies for the discovery of asymmetric organocatalysts rely primarily upon trial and error. Our goal is to systematically study steric and electronic effects on the reactivity of pyrrolidine organocatalysts by examining the ability of the catalysts to generate enamines with α-substituted aldehydes and ketones. α-Substituted aldehydes and ketones are the products of organocatalyzed reactions, and enamine formation of these products should lead to undesirable epimerization of the stereocenter. We report the synthesis of enantiomerically enriched α-substituted aldehyde and ketone model compounds, the development of assays for monitoring their enantiomeric excess, and the preliminary evalaution of 2-substitued pyrrolidine organocatalysts.