Natural product total synthesis, as a field, has sought to provide access to complex and intriguing structures as a means to further chemical knowledge, support biological studies and inspire therapeutic design. However, such access is limited by the tools made available to synthetic chemists, and as such, a leading goal within the community is the development and application of novel reactions to expedite the synthesis of targets of interest. Over the years the chemical toolbox, as it is informally known, has been consistently expanded from more traditional functional group interconversions and strategies, to reactions which can rapidly introduce stereochemical complexity and those which promote activation of chemical bonds typically viewed as inert. The dissertation herein reports the study of reactions which take achiral materials or materials with minimal chiral elements and rapidly introduce molecular complexity in both hydrocarbon and heterocyclic frameworks.