Distinct chemical factors in hydrolytic reactions catalyzed by metalloenzymes and metal complexes
Leonardo F. Serafim, Vindi M. Jayasinghe‐Arachchige, Lukun Wang, Parth Rathee, Jiawen Yang, Sreerag N. Moorkkannur, Rajeev Prabhakar
Abstract
nucleophilicity and Lewis acid activation, respectively. In synthetic analogues, hydrolysis is facilitated by the inclusion of a second metal center, hydrophobic effects, a biological metal (Zn, Cu and Co) and a terminal hydroxyl nucleophile. Due to the absence of the protein environment, hydrolysis by these small molecules is exclusively influenced by nucleophile activation. The results gleaned from these studies will enhance the understanding of fundamental principles of multiple hydrolytic reactions. They will also advance the development of computational methods as a predictive tool to design more efficient catalysts for hydrolysis, Diels-Alder reaction, Michael addition, epoxide opening and aldol condensation.