UCLA

About 2.7% of the 187 years spent researching ozone are encapsulated in this dissertation. The main goal of the research conducted was to improve dealkenylation, an emerging organic chemistry method for synthesis through C(sp3)–C(sp2) bond scission. The first generation of dealkenylation required the use of ozone to generate a high-energy peroxide intermediate which enabled radical cascades to break bonds and create new, valuable products. A second generation was developed through this work to bypass the ozone requirement and thereby diversify the chemical space available to dealkenylation. Not only did this second generation solve issues regarding incompatibilities of alkenes with ozone, but also it broadened the products available after radical functionalization. Further research into the ozonolysis reaction led to the development of a predictive tool to quantify the dealkenylation peroxide intermediate and provide a more complete understanding of the overall transformation. Additionally, two new transformations involving ozone were uncovered. The first applies dealkenylation to cycloalkanones to access their 1-carbon deleted analoges. Samarium iodide was the key to both initiate the radical cascade and to reform the ring after carbon excision. The second is the ozonolysis of a C–C sigma-bond. The bridging C–C sigma-bond of a bicyclo[1.1.0]butane and a bicyclo[2.1.0]pentane was activated to enable radical addition of ozone. Computational studies predicted two mechanistic pathways, of which the major supports the formation of a 1,2,3-trioxane, which has never been realized in a flask. Chapters one, two, and four originate from review articles that provide background on the field of peroxide chemistry (chapter one), and present day dealkenylation (chapter two and chapter four). Chapters two and four are each included with permission from the first authors. Chapter three introduces the second generation of ozone-free dealkenylation. Chapter five offers solutions to enable ozonation of some compound classes previously thought to be incompatible. Chapter six discusses the experimental work completed to generate the dataset for the machine learning model to quantify ozonolysis products. Chapter seven provides a proof of concept for the dealkenylative ring contraction strategy. Finally, chapter eight reveals the first ozonolysis of C–C sigma-bonds. Overall, this research advances the dealkenylation methodology, expanding into ozone-free techniques, predictive tools, and new atom-editing strategies. This work culminates with the discovery of C–C sigma-bond ozonolysis.