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An Artificial Heme Enzyme for Cyclopropanation Reactions |
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| Authors: | Dr Lara Villarino Prof Kathryn E Splan Dr Eswar Reddem M?Sc Lur Alonso‐Cotchico M?Sc Cora Gutiérrez?de?Souza Prof Agustí Lledós Prof Jean‐Didier Maréchal Dr Andy‐Mark W H Thunnissen Prof Gerard Roelfes |
| Affiliation: | 1. Stratingh Institute for Chemistry, University of Groningen, AG, Groningen, The Netherlands;2. Department of Chemistry, Macalester College, Saint Paul, MN, USA;3. Departament de Química, Universitat Autònoma de Barcelona, Barcelona, Spain;4. Groningen Biomolecular Sciences and Biotechnology Institute, University of Groningen, AG, Groningen, The Netherlands |
| Abstract: | An artificial heme enzyme was created through self‐assembly from hemin and the lactococcal multidrug resistance regulator (LmrR). The crystal structure shows the heme bound inside the hydrophobic pore of the protein, where it appears inaccessible for substrates. However, good catalytic activity and moderate enantioselectivity was observed in an abiological cyclopropanation reaction. We propose that the dynamic nature of the structure of the LmrR protein is key to the observed activity. This was supported by molecular dynamics simulations, which showed transient formation of opened conformations that allow the binding of substrates and the formation of pre‐catalytic structures. |
| Keywords: | artificial metalloenzymes biocatalysis carbenes enzyme design heme enzymes |
