UC Davis

This dissertation describes two projects in the organic chemistry field centering around the stereoselective synthesis of trisubstituted benzodihydrofurans and related natural products through C–H insertion of donor/donor carbenes into stereogenic centers. The first chapter reports the development of a stereoselective methodology to make 2,2,3-trisubstituted benzodihydrofurans. The method expands intramolecular C–H insertion reactions with donor/donor carbenes to stereogenic insertion centers, thereby enabling benzodihydrofuran formation in high diastereoselectivity and enantioselectivity. Computational studies on the system illuminate the origins of divergent stereochemical outcomes for different substrate classes. The second chapter applies this methodology to the asymmetric synthesis of two dihydrobenzoxanthone natural products, cycloartobiloxanthone and artoindonesianin Z-2. First, an introduction to the natural product subclass outlines structural variations and biosynthetic pathways for the isolated natural products found in the family and their reported biological activities. Progress towards the synthesis of these two natural products is split into three main stages. The first stage reports a first-generation route and its related benzylic oxidation roadblock. The second stage details numerous route-scouting endeavors. The third stage outlines a second-generation route and future work toward completing the asymmetric synthesis of cycloartobiloxanthone and artoindonesianin Z-2.