A Co(TAML)-based artificial Metalloenzyme for asymmetric group transfer catalysis Eva Meeus 1 , Nico V. Igareta 2 , Iori Morita 2 , Thomas R. Ward 2 , Bas de Bruin 1 , Joost N.H. Reek 1 1 University of Amsterdam, Netherlands, 2 University of Basel, Switzerland Second coordination sphere effects are crucial for the function of enzymes and hence laid the foundation for an intensive and thriving area of research devoted to catalysis in confined spaces. For instance, transition metal complexes can be placed inside synthetic cages to control their catalytic properties. Alternatively, encapsulation inside a protein also affords a well-defined secondary coordination sphere. The resulting artificial metalloenzyme offers means to optimize selectivity and activity towards a desired reaction. In this work, we incorporated a biotinylated Co(TAML)-complex (TAML = Tetra Amido Macrocyclic Ligand) into streptavidin (Sav) to assemble an artificial metalloenzyme, which is active in oxygen atom transfer to aromatic olefins. After careful characterization of the host–guest system, initial screening of the Sav library—that included (double) mutations at the positions Sav S112X and Sav K121X—demonstrated a positive effect on the selectivity, which is otherwise not achieved in absence of the protein. Hence, the Co(TAML)-catalyst proves amenable to the design and optimization of an artificial metalloenzyme active in asymmetric group transfer catalysis, by means of the biotin-streptavidin technology. References 1. E.J. de Vries, D.B. Janssen, Curr. Opin. Biotechnol. 2003 , 14, 414–420. 2. N.P. van Leest, M.A. Tepaske, J.-P.H. Oudsen, B. Venderbosch, N.R. Rietdijk, M.A. Siegler, M. Tromp, J.I. van der Vlugt, B. de Bruin, J. Am. Chem. Soc. 2020 , 142, 552−563. 3. F. Schwizer, Y. Okamoto, T. Heinisch, Y. Gu, M.M. Pellizzoni, V. Lebrun, V. Köhler, J.C. Lewis, T.R. Ward, Chem. Rev . 2018 , 118 , 142–231. 4. J. Serrano-Plana, C. Rumo, J.G. Rebelein, R.L. Peterson, M. Barnet, T.R. Ward, J. Am. Chem. Soc. 2020 , 142 , 10617– 10623.
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