Analysing the Reactivity and Mechanisms of Artificial Substrates for Biological Catalysts

It has recently been noted that enzymes can be promiscuous in their activity, and catalyse the reactions of a range of functional groups, including those not found in natural systems. Defining the fundamental details of these reactions will assist in understanding the chemical basis for this observation. This thesis describes phosphoryl and sulfuryl transfer reactions, using Free Energy Relationship (FER) to investigate their transition states.