Herein, we discuss our laboratory's research in the activation of alcohol derivatives in cross-coupling and cross-electrophile coupling reactions. Our developed methods enable the use of secondary alcohols to afford tertiary stereogenic centers, which we applied to the synthesis of pharmaceutically relevant compounds and substructures. We first discuss the synthesis of bioactive compounds via stereospecific Kumada cross-coupling reactions, followed by a discussion on the development of our stereoselective cross-electrophile coupling reaction to synthesize cyclopropanes.