This thesis presents the development of an efficient catalytic asymmetric olefin haloamidation method and mechanistic investigations of intermolecular halofunctionalization reactions. It guides the reader through the challenges of catalytic asymmetric olefin halofunctionalization and presents how our group has used a mechanistically conscious approach to solve these problems to achieve high enantiocontrol over a stereodefined carbon-halogen bond. Chapter 1 focuses on the development of a catalytic asymmetric Ritter-type haloamidation of olefins. The stereodefined vicinal haloamine moiety is highly valuable; however, catalytic asymmetric variations have not realized the same success as analogous haloetherification and dihalogenation reactions. We utilize Halenium Affinity to examine the core difficulties of haloaminations and design a competent nucleophile for this transformation. Chapter 2 gives the reader a more accurate mechanistic understanding of intermolecular olefin halofunctionalizations. This reaction is often depicted as a stepwise mechanism with the formation of a haliranium ion that is then intercepted by a nucleophile to provide the difunctionalized product. Preliminary mechanistic evidence suggests a spectrum of concerted vs. stepwise mechanisms dependent on the alkene, halenium ion, halenium donor, and nucleophile.
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