The creation of new carbon–carbon bonds with a high degree of stereocontrol is a powerful strategy employed in targeted synthesis of complex organic molecules. Chiral benzene-fused 5-membered rings represent a significant portion of medicinally relevant molecules. This dissertation describes the construction of benzodihydrofurans, indanes and indolines by C–H insertion reactions of donor/donor carbenes. Chapter one discusses the development of a stereochemcially predicative model for insertion reactions to form benzodihydrofurans. From this study, a predictive model for diastereoselecitivty was established. Chapter two discusses methodology development for insertion reactions to make indolines and indanes. These cores were produced in high yields, with a high degree of stereocontrol and functional group tolerance.