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Artificial Enzymes

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An original concept called “Artificial metalloenzymes” has recently emerged at the border between organometallic and enzymatic catalysis, in which biomacromolecules (proteins, DNA) act as hosts to metallic species (ions, coordination or organometallic complexes) affording new hybrid catalysts with unprecedented reactivities. At the laboratory, several half-sandwich complexes of Ru(II) et de Rh(III) including various diimine ligands and a specific chemical function allowing their covalent anchoring to cysteine 25 of papain chosen as protein host. Modified papain acquires Diels-Alderase, formate dehydrogenase or transfer hydrogenase activities according to the metallic cofactor introduced within the protein scaffold.


  • B. Talbi, P. Haquette, A. Martel, F. de Montigny, C. Fosse, S. Cordier, T. Roisnel, G. Jaouen, and M. Salmain. (2010) (η6-arene) ruthenium(II) complexes and metallo-papain hybrid as Lewis acid catalysts of Diels-Alder reaction in water, Dalton Trans. 39, 5605-5607.
  • P. Haquette, B. Talbi, L. Barilleau, N. Madern, C. Fosse, and M. Salmain. (2011) Chemically engineered papain as artificial formate dehydrogenase for NAD(P)H regeneration, Org. Biomol. Chem. 9, 5720 - 5727.
  • A. Chevalley, and M. Salmain. (2012) Enantioselective transfer hydrogenation of ketone catalysed by artificial metalloenzymes derived from bovine b-lactoglobulin, Chem. Commun. 48, 11984-11986.

Design of artificial metalloenzymes for asymmetric catalysis in environmentally-benign conditions

The aim of the project was to design artificial metalloenzymes from supramolecular assembling between a protein host (bovine beta-lactoglobulin, bLG) and a metal complex containing a prochiral hemilabile ligand so as to catalyze reactions in aqueous medium in a stereoselective fashion. A series of palladium(II) complexes of prochiral hemilabile NCN pincer ligands was synthesized some of which from docking studies so as to ensure a strong affinity between the metal complex and bLG. We showed that some of these assemblies were able to catalyze aldol condensation reactions with unusual diastereoselectivity for the cis condensation product.

“Very Important Paper” L. Pocquet, N. Vologdin, G. F. Mangiatordi, I. Ciofini, O. Nicolotti, S. Thorimbert, and M. Salmain. (2017) Supramolecular anchoring of NCN-pincer palladium complexes into a beta-barrel protein host. Molecular docking and reactivity insights, Eur. J. Inorg. Chem., 3622–3634. DOI : 10.1002/ejic.201700365. Ref HAL : hal-01585231.