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Development of original catalysts

Published on 24 January 2019

Dr. Olivier Hamelin
Laboratoire Chimie et Biologie des Métaux
17 avenue des Martyrs
38 054 Grenoble Cedex 09

Phone: 04 38 78 91 08

Chiral-at-metal catalyst

During the last decade we were interested in the development of homogeneous and heterogeneous metal-based catalysts for the oxidation of organic substrates. Some ruthenium and manganese-based systems reported by our group shown interesting ability to perfom sulfide and/or alkene oxidations [1, 5, 7, 8].

Chiral-at-metal catalyst

Usually chiral catalysts are formed by a metal cation (usually, Mn, Cu, Ti…) surrounded by an organic chiral ligand responsible of the asymmetric induction. Our group is also specialized in the development of synthetic technics (resolution and asymmetric transformation) for the preparation of enantiopure chiral-only-at-metal complexes and their use in asymmetric catalysis [2, 3]. As an exemple, we shown, for the first time that a chiral-at-metal complex without any chiral organic ligand, and in which the catalytic center is also the stereogenic one, can be used for asymmetric catalysis without any racemization [2, 4]. Recently, an evolution of our research program was to design chiral-at-metal complexes so that they displayed free coordinating moieties for binding a second metal ion on which the reaction could take place. This original and pioneer strategy was promoted by the development of a chiral-at-metal homodinuclear complex for catalytic asymmetric transfer hydrogenation to ketones [6].

Development of eco-aware photocatalysts for oxidation

Based on this strategy, and with the care to develop ever greener and more economical chemistry our current research interest concerns the development of new eco-aware light-driven catalytic oxidation processes using water as the unique oxygen atom source. Two differents dyads constituted by the assembly of a photosensitizer and a catalytic fragment within the same entity were developed. Upon irradiation, both complexes were able to catalyze selective sulfide oxygenation involving an oxygen atom transfer from the water molecule to the substrate associated to a proton-coupled electron transfer (PCET) yielding to a high valent oxidant Ru(IV) oxo species [10].

Synthesis of selectively labelled precursors and amino acids for real-time studies of biological nano-proteins by NMR
This project, in collaboration with the group of Dr J. Boisbouvier (Institut de Biologie Structurale, Grenoble) involves the regiospecific labelling (2H, 13C) of amino acids such as leucine, valine and isoleucine by incorporation of synthesized labelled acetolactacte precursor in the metabolic pathway. This new labelling allows stereospecific assignment of methyl groups, extraction of precise long-range structural restraints and without any doubt will bring informations about interactions in large proteins [9, 11, patent].



Iali W, Lanoe PH, Torelli S, Jouvenot D, Loiseau F, Lebrun C, Hamelin O and Ménage S

A Ruthenium(II)-Copper(II) dyad for the photocatalytic oxygenation of organic substrates mediated by dioxygen activation.
Angewandte Chemie - International Edition, 2015, 54(29): 8415-8419

Kerfah R, Plevin MJ, Pessey O, Hamelin O, Gans P and Boisbouvier J
Scrambling free combinatorial labeling of alanine-β, isoleucine-δ1, leucine-proS and valine-proS methyl groups for the detection of long range NOEs.
Journal of Biomolecular NMR, 2015, 61(1): 73-82


Guillo P, Hamelin O, Pécaut J and Ménage S
Complexation to [Ru(bpy)
2]2+: The trick to functionalize 3,3'-disubstituted-2,2'-bipyridine.
Tetrahedron Letters, 2013, 54(8): 840-842

Hajj Chehade M, Loiseau L, Lombard M, Pecqueur L, Ismail A, Smadja M, Golinelli-Pimpaneau B, Mellot-Draznieks C, Hamelin O, Aussel L, Kieffer-Jaquinod S, Labessan N, Barras F, Fontecave M and Pierrel F
ubiI, a new gene in Escherichia coli Coenzyme Q biosynthesis, is involved in aerobic C5-hydroxylation.
Journal of Biological Chemistry, 2013, 288(27): 20085-20092

Mas G, Crublet E, Hamelin O, Gans P and Boisbouvier J

Specific labeling and assignment strategies of valine methyl groups for NMR studies of high molecular weight proteins.
Journal of Biomolecular NMR, 2013, 57(3): 251-262


Ayala I, Hamelin O, Amero C, Pessey O, Plevin MJ, Gans P and Boisbouvier J
An optimized isotopic labelling strategy of isoleucine-γ
2 methyl groups for solution NMR studies of high molecular weight proteins.
Chemical Communications (Camb), 2012, 48(10): 1434-1436

Chan A, Clémancey M, Mouesca JM, Amara P, Hamelin O, Latour JM and Ollagnier de Choudens S
Studies of inhibitor binding to the [4Fe-4S] cluster of quinolinate synthase.
Angewandte Chemie International Edition, 2012, 51(31): 7711-7714

Guillo P, Hamelin O, Batat P, Jonusauskas G, McClenaghan ND and Ménage S
Photocatalyzed sulfide oxygenation with water as the unique oxygen atom source.
Inorganic Chemistry, 2012, 51(4): 2222-2230


Gans P, Ayala I, Boisbouvier J and Hamelin O
Process for the specific isotopic labeling of methyl groups of Val, Leu and Ile.
WO/2011/083356 (Patent issued on 07/14/2011).

Hamelin O, Guillo P, Loiseau F, Boissonnet MF and Ménage S
A dyad as photocatalyst for light-driven sulfide oxygenation with water as the unique oxygen atom source.
Inorganic Chemistry, 2011, 50(17): 7952-7954

Plevin MJ, Hamelin O, Boisbouvier J and Gans P
A simple biosynthetic method for stereospecific resonance assignment of prochiral methyl groups in proteins.
Journal of Biomolecular NMR, 2011, 49 (2): 61-67


Gans P, Hamelin O, Sounier R, Ayala I, Durá MA, Amero CD, Noirclerc-Savoye M, Franzetti B, Plevin MJ and Boisbouvier J
Stereospecific isotopic labeling of methyl groups for NMR spectroscopic studies of high-molecular-weight proteins.
Angewandte Chemie (International Ed. in English), 2010, 49(11): 1958-1962

Guillo P, Hamelin O, Loiseau F, Pecaut J and Ménage S
Synthesis, electrochemical and photophysical properties of heterodinuclear Ru-Mn and Ru-Zn complexes bearing ambident Schiff base ligand.
Dalton Transactions, 2010, 39(24): 5650-5657

Pierrel F, Hamelin O, Douki T, Kieffer-Jaquinod S, Mühlenhoff U, Ozeir M, Lill R and Fontecave M
Involvement of mitochondrial ferredoxin and para-aminobenzoic acid in yeast coenzyme Q biosynthesis.
Chemistry & Biology, 2010, 17(5): 449-459


Calmettes S, Albela B, Hamelin O, Ménage S, Miomandre F and Bonneviot L
Multistep Anchoring of a catalytically active rutherium complex in porous mesostructured silica.
New Journal of Chemistry, 2008, 32: 727-737

Hamelin O, Ménage S, Charnay F, Chavarot M, Pierre JL, Pecaut J and Fontecave M
New polydentate ligand and catalytic properties of the corresponding ruthenium complex during sulfoxidation and alkene epoxidation.
Inorganic Chemistry, 2008, 47(14): 6413-6420


Hamelin O, Rimboud M, Pecaut J and Fontecave M
Chiral-at-metal ruthenium complex as a metalloligand for asymmetric catalysis.
Inorganic Chemistry, 2007, 46: 5354-5360

Soudiresane T, Selvakumar S, Ménage S, Hamelin O, Fontecave M and Singh AP
Ru- and Fe- based N,N'-bis(2-pyridylmethyl)-N-methyl-(1S,2S)-1,2-cyclohexanediamine complexes immobilised on mesoporous MCM-41: Synthesis, characterization and catalytic applications.
Journal of Molecular Catalysis A - Chemical, 2007, 270: 132-143


Fontecave M, Hamelin O and Ménage S
Chiral-at-metal complexes as asymmetric catalysts.
Topics in Organometallic Chemistry, 2005, 15: 27


Hamelin O, Pécaut J and Fontecave M
Crystallization-induced asymmetric transformation of chiral-at-metal ruthenium (II) complexes bearing achiral ligands.
Chemistry - A European Journal, 2004, 10(10): 2548-2554


Chavarot M, Ménage S, Hamelin O, Charnay F, Pecaut J and Fontecave M
"Chiral-at-Metal" octahedral ruthenium(II) complexes with achiral ligands: A new type of enantioselective catalyst.
Inorganic Chemistry, 2003, 42(16): 4810-4816

Schoumacker S, Hamelin O, Pécaut J and Fontecave M
Catalytic asymmetric sulfoxidation by chiral manganese complexes: Acetylacetonate anions as chirality switches.
Inorganic Chemistry, 2003, 42: 8110-8116