Research, developed at the Laboratory of Organic Pharmaceutical Chemistry of the School of Pharmacy, UMR-CNRS 6517, is centred on the synthesis of novel therapeutic compounds using monoelectronic transfer reactions. Tetrakis(dimethylamino)ethylene (TDAE) is a powerful electron donor which has the specific property of activating the carbon-halogen bond leading to the formation of a stable electrophilic radical and a stable neutrophilic anion. Since 2002, our team has developed a program using monoelectronic transfer reactions initiated by TDAE of nitroaromatic, nitroheterocyclic and quinonic bioreducible alkylating agents. The goal is to synthesize new therapeutic compounds for use as anti-infectious agents, anticancer agents, and agents active on the central nervous system. In this context, we present the first pharmacochemical tools obtained with this strategy during reactions between diverse electrophilic compounds (aldehydes, ketones, alpha-keto-esters, ketomalonates, alpha-ketolactames, ...) and benzylic anions formed in situ by the action of TDAE. We illustrate the usefulness of this strategy by describing the preparation of new compounds of biological interest and the associated pharmacomodulation work.