Computational Studies of Metal Free C−H Bond Functionalization

Carbon–hydrogen bond functionalization reactions can greatly facilitate chemical synthesis due to their capability to increase molecular complexity from readily available starting materials with minimal waste generation. These processes are most often achieved through transition metal catalysis, though metal-free approaches for such reactions are becoming increasingly common. DDQ and hypervalent iodine reagents have shown to be greatly useful for promoting C–H cleavage. DFT calculations presented in this dissertation were performed to study the mechanistic pathways of metal free C–H functionalization mediated by DDQ and various hypervalent iodine reagents. These computational investigations not only replicate and explain the experimental observations, but also provide a better understanding of the reaction mechanisms and factors contributing to the reactivity and selectivity. These computational insights were used to develop a predictive reactivity model for the DDQ-mediated C–H functionalization.