Analysis of historical data in the pharmaceutical industry has shown a positive correlation between Fsp3 (the fraction of a molecule with sp3 hybridized bonds) and clinical success. With increased interest in the synthesis of compounds with higher Fsp3, there has been a renewed interest in the broader chemistry community in methods for the installation of these saturated moieties. However, formation as well as functionalization of Csp3 bonds represent some of the most challenging transformations in organic chemistry. Visible light-mediated transformations have become increasingly more popular in recent years as a tool for the formation of these difficult bonds. Photochemistry offers a mild approach to the formation and utilization of alkyl radicals in a wide range of settings, affording a broad range of possible products. Firstly, photoredox catalysis harnesses radicals in a controlled, predicable manner and can be used to orchestrate elaborate radical and polar bond-forming processes, allowing for the development of radical-polar crossover (RPC) reactions. Herein, two separate RPC reactions are explored: a dicarbofunctionalization reaction, furnishing complex carbon skeleton frameworks, as well as a carbo-sulfamoylation reaction, furnishing pharmaceutically relevant alkyl sulfonamide moieties. Furthermore, metallaphotoredox, also known as photoredox/nickel dual catalysis, can be used to develop a wide array of cross-coupling chemistry. Through the use of thianthrenium salts as a new handle for functionalization, dual catalysis approaches to the alkylation and aminomethylation of these salts are explored herein.