UC Berkeley

The following dissertation discusses the development, study, and applications of transition-metal-catalyzed substitution reactions to provide enantioenriched tertiary alkyl fluorides. These reactions constitute some of the first enantioselective substitutions of fluoroalkenes and the first examples of the enantioselective desymmetrization of difluoromethylene groups. Several of these reactions define new strategies for the controlled activation of C–F bonds. Mechanistic studies have revealed several unique aspects of the stability, reactivity, and stereochemistry of fluorinated organometallic intermediates, revealed the turnover-limiting and enantiodetermining steps in Ir-catalyzed C–F activation reactions, and highlighted the powerful effects of bimetallic cooperation in C–F activation reactions. In the final chapter, we discuss the contrathermodynamic isomerization of olefins by a tandem process.