Origins of High-Activity Cage-Catalyzed Michael Addition.

ABSTRACT: Cage catalysis continues to create significant interest, yet catalyst function remains poorly understood. Herein, we report mechanistic insights into coordination-cage-catalyzed Michael addition using kinetic and computational methods. The study has been enabled by the detection of identifiable catalyst intermediates, which allow the evolution of different cage species to be monitored and modeled alongside reactants and products. The investigations show that the overall acceleration results from two distinct effects. First, the cage reaction shows a thousand-fold increase in the rate constant for the turnover-limiting C-C bond-forming step compared to a reference state. Computational modeling and experimental analysis of activation parameters indicate that this stems from a significant red

SUBMITTER: Boaler PJ 

PROVIDER: S-EPMC11258793 | biostudies-literature | 2024 Jul

REPOSITORIES: biostudies-literature