Yoann ROUSSELIN
@icmub.com
Research Engineer
ICMUB
Scopus Publications
Scopus Publications
Jérôme Bayardon, Chen Qian, Raluca Malacea-Kabbara, Yoann Rousselin, and Sylvain Jugé
American Chemical Society (ACS)
An enantioselective synthesis of a new class of benzophosphole-based heterocycles bearing a fused triazole ring with enantioselectivities of ≤99% is reported. The key steps of the synthesis are based on an innovative stereospecific phosphinyl N → O migration of aminophosphine-boranes into phosphinites, followed by an intramolecular cyclization. Five X-ray structures of P-chirogenic triazolobenzophospholes and a gold(I) complex were established, for assigning absolute configurations, the stereochemistry of the reactions, and the placement of the triazole substituent at the syn position of the P center.
Yoann Rousselin and Alexandre Clavel
International Union of Crystallography (IUCr)
The structure of pinaverium bromide (systematic name: 4-[(2-bromo-4,5-dimethoxyphenyl)methyl]-4-{2-[2-(6,6-dimethyl-2-bicyclo[3.1.1]heptanyl)ethoxy]ethyl}morpholin-4-ium bromide; C26H41Br2NO4), was determined at 110 K. It has monoclinic (P21) symmetry. It is of interest with respect to its anti-inflammatory properties. The asymmetric unit contains two independent molecules, one of which exhibits disorder of the bicyclo terminal group (occupancy factors: 0.78 and 0.22).
Simon Larsen, Joseph A. Adewuyi, Kolle E. Thomas, Jeanet Conradie, Yoann Rousselin, Gaël Ung, and Abhik Ghosh
American Chemical Society (ACS)
Phlorins have long remained underexplored relative to their fully conjugated counterparts, such as porphyrins, hydroporphyrins, and corroles. Herein, we have attempted to bridge that knowledge gap with a scalar-relativistic density functional theory (DFT) study of unsubstituted iridium and gold phlorin derivatives and a multitechnique experimental study of iridium-bispyridine and gold complexes of 5,5-dimethyl-10,15,20-tris(pentafluorophenyl)phlorin. Theory and experiments concur that the phlorin derivatives exhibit substantially smaller HOMO–LUMO gaps, as reflected in a variety of observable properties. Thus, the experimentally studied Ir and Au complexes absorb strongly in the near-infrared (NIR), with absorption maxima at 806 and 770 nm, respectively. The two complexes are also weakly phosphorescent with emission maxima at 950 and 967 nm, respectively. They were also found to photosensitize singlet oxygen formation, with quantum yields of 40 and 28%, respectively. The near-infrared (NIR) absorption and emission are consonants with smaller electrochemical HOMO–LUMO gaps of ∼1.6 V, compared to values of ∼2.1 V, for electronically innocent porphyrins and corroles. Interestingly, both the first oxidation and reduction potentials of the Ir complex are some 600 mV shifted to more negative potentials relative to those of the Au complex, indicating an exceptionally electron-rich macrocycle in the case of the Ir complex.
Michael Knorr, Lydie Viau, Lena Knauer, Carsten Strohmann, Yoann Rousselin, and Marek M. Kubicki
Royal Society of Chemistry (RSC)
The self-assembly of acetylenic dithioethers with CuX salts produces coordination polymers, some of them being halogenated across the triple bond.
Adrien T. Normand, Yue Wu, Tiffanie Régnier, Paul Fleurat‐Lessard, Yoann Rousselin, Benjamin Théron, Pierre Le Gendre, and Mariolino Carta
Wiley
AbstractPoly(vinyl chloride) undergoes dechlorination in the presence of triethylsilane (Et3SiH) and a catalytic amount of [Cp2Zr(NPh2)][CH3B(C6F5)3] (1 b) at 40–80 °C, with up to 91 % efficiency. Stoichiometric reactivity studies conducted on cyclohexyl chloride as a model suggest that 1 b dechlorinates PVC by initial chloride abstraction, followed by hydride transfer to the cationic PVC chain from Et3SiH. Consumer items such as pipe fitting, vinyl disc or electric cable insulation undergo either dechlorination or hydrosilylation of the carbonyl‐containing copolymer (polyvinyl acetate) or plasticizer (phthalate).
Azhar Kechiche, Shaymaa Al Shehimy, Lhoussain Khrouz, Cyrille Monnereau, Christophe Bucher, Stephane Parola, Alla Bessmertnykh-Lemeune, Yoann Rousselin, Andrey V. Cheprakov, and Habib Nasri
Royal Society of Chemistry (RSC)
Incorporating phosphonate groups onto the phenyl substituents of meso-tetraphenylporphyrins proves advantageous for their utilization in photocatalysis.
Ying Jin, Zhiyong Chai, Yoann Rousselin, Jean-Thomas Pouzens, Paul Fleurat-Lessard, Claude P. Gros, Annaëlle Beau, Frédéric Bolze, and Hai-Jun Xu
Elsevier BV
Antonin Jaillet, Jérôme Bayardon, Yoann Rousselin, and Sylvain Jugé
American Chemical Society (ACS)
In the recent past, the chirality borne by a phosphorus center has aroused growing interest in many fields, and the development of new methodologies, notably using inexpensive reagents and simple experimental conditions, has become topical. An efficient stereoselective synthesis of P-chirogenic phosphinites useful as chiral phosphorus building blocks is herein described thanks to a new intramolecular phosphorus rearrangement based on P*(III)-phosphinyl N→O migration. This rearrangement was performed by heating at 50 °C aminophosphine-boranes, easily prepared from chiral amino alcohols, with DABCO in toluene overnight. Twenty-seven P-chirogenic phosphinites and borane complexes were thus prepared in yields up to 89%. The crude P*(III)-phosphinites were in situ used in stereoselective synthesis of P-chirogenic aminophosphine-phosphinites, phosphinothioates, sec- and tert-phosphine-oxides, and mono- and diphosphines in overall yields ranging from 28 to 89% and with e.e. up to 99%. Twenty-one X-ray structures of P-chirogenic compounds were established, allowing us to attribute undoubtedly their absolute configuration and the stereochemistry of the reactions. Finally, new ferrocenyl-bridged diphosphine ligands synthesized from P*(III)-chirogenic diphosphinites were tested in asymmetric metal-catalyzed reactions, providing enantioselectivities up to 95% e.e. in allylation of α-naphthylmethylamine at room temperature. To conclude, this rearrangement opens up an efficient new way for the stereoselective synthesis of numerous classes of P-chirogenic phosphorus compounds, notably bearing bulky substituents.
Valentin Vaillant-Coindard, Florian Chotard, Benjamin Théron, Cédric Balan, Jérôme Bayardon, Raluca Malacea-Kabbara, Ewen Bodio, Yoann Rousselin, Paul Fleurat-Lessard, and Pierre Le Gendre
American Chemical Society (ACS)
Ethylene- and phenylene-bridged bis(salicylamidine) ligands have been readily prepared from ethylene or phenylenediamine and iminium chloride derivatives generated in situ from N,N-dialkylsalicylamides. The former, in its diprotonated form (FAlenH2), reacts with AlMe3 to afford a zwitterionic dimethyldiphenoxyaluminate complex with the FAlen ligand monoprotonated and in a bidentate κ2O,O' fashion. A phenylene-bridged proligand behaves differently, yielding a neutral methylaluminum complex bearing a κ3O,N,O'-coordinated FAlen ligand. From these complexes, methyl anion abstraction with B(C6F5)3 or a reaction with Schrock's alcohol leads to the corresponding aluminum cationic or alkoxy complexes in which a κ4O,N,N',O'-coordination mode of the FAlen ligand is observed. X-ray diffraction studies of the proligands and of the complexes show that the amidine functions feature a trans configuration when the N-amidine atom is not coordinated to the metal and conversely a cis configuration when it is. Density functional theory calculations show that trans-cis isomerization of the amidine functions occurs upon coordination with the metal ion with very low energy barriers. They also confirm the intuition that the denticity of the FAlen ligands in the complexes is directly related to the electron richness of the metal ion. At last, FAlen Al complexes are used as initiators for the controlled ring-opening polymerization of rac-lactide to afford poly(lactic acid) with slight isotactic bias.
Pawel Jewula, Mickaël Grandmougin, Mélanie Choppin, Anna Maria Chiara Tivelli, Agnese Amati, Yoann Rousselin, Lydia Karmazin, Jean‐Claude Chambron, and Michel Meyer
Wiley
AbstractSix‐ and seven‐membered cyclic hydroxamic acids are found as terminal binding units in different families of siderophores, including exochelins and mycobactins. The simplest models of these preorganized chelating ligands were known, but their coordination chemistry with Fe3+, the target metal ion of siderophores, had never been reported. Four complexes were synthesized and studied: two Fe3+ complexes, one with the six‐membered ring hydroxamate PIPO− and one with the seven‐membered ring hydroxamate AZEPO−, and the two corresponding Ga3+ complexes. X‐ray diffraction studies showed that the interligand repulsion energies were better minimized in the case of the AZEPO− complexes whatever the metal cation considered, and that the Fe−O bond distances were shorter in [Fe(AZEPO)3] by comparison with [Fe(PIPO)3].
Amélie Godard, Laura Abad Galán, Jean Rouillon, Shaymaa Al Shehimy, Wassima Tajani, Charlotte Cave, Raluca Malacea-Kabbara, Yoann Rousselin, Pierre Le Gendre, Arnaud Fihey,et al.
American Chemical Society (ACS)
Aza-boron-dipyrromethenes (Aza-BODIPYs) are an increasingly studied class of fluorophores. They can be seen as an azadipyrromethene ("aza-DIPY") ligand rigidified by a metalloid, a boron atom. Based on this idea, a series of complexes of group 13 metals (aluminum and gallium) have been synthesized and characterized. The impact of the metal and of the nature of the substituents of aza-DIPY core were investigated. The photophysical and electrochemical properties were determined, and an X-ray structure of an azaGaDIPY was obtained. These data reveal that azaGaDIPY and azaAlDIPY exhibit significant red-shifted fluorescence compared to their analogue aza-BODIPY. Their emission can go up to 800 nm for the maximum emission length and up to NIR-II for the emission tail. This, associated with their electrochemical stability (no metal release whether oxidized or reduced) makes them a promising class of fluorophores for optical medical imaging. Moreover, X-ray structure and molecular modeling studies have shown that this redshift seems to be more due to the geometry around the boron/metal than to the nature of the metal.
Benjamin Théron, Valentin Vaillant-Coindard, Cédric Balan, Yoann Rousselin, Jérôme Bayardon, Raluca Malacea-Kabbara, and Pierre Le Gendre
Royal Society of Chemistry (RSC)
Here we report the synthesis, characterization, and evaluation in LA ROP catalysis of a series of Zn(ii) and Al(iii) complexes associated with a new generation of phenoxy-amidine ligands forming 5-membered metallacycles.
Valentin Vaillant-Coindard, Benjamin Théron, Gaël Printz, Florian Chotard, Cédric Balan, Yoann Rousselin, Philippe Richard, Iogann Tolbatov, Paul Fleurat-Lessard, Ewen Bodio,et al.
American Chemical Society (ACS)
Yi Wang, Yoann Rousselin, Claude P. Gros, Frédéric Bolze, Xu Liang, Weihua Zhu, and Haijun Xu
Elsevier BV
Daniel Szczerba, Davin Tan, Jean-Louis Do, Hatem M. Titi, Siham Mouhtadi, Denis Chaumont, María del Carmen Marco de Lucas, Nicolas Geoffroy, Michel Meyer, Yoann Rousselin,et al.
American Chemical Society (ACS)
Colloidal bismuth therapeutics have been used for hundreds of years, yet remain mysterious. Here we report an X-ray pair distribution function (PDF) study of the solvolysis of bismuth disalicylate, a model for the metallodrug bismuth subsalicylate (Pepto-Bismol). This reveals catalysis by traces of water, followed by multistep cluster growth. The ratio of the two major species, {Bi9O7} and {Bi38O44}, depends on exposure to air, time, and the solvent. The solution-phase cluster structures are of significantly higher symmetry in comparison to solid-state analogues, with reduced off-center Bi3+ displacements. This explains why such "magic-size" clusters can be both stable enough to crystallize and sufficiently labile for further growth.
Ali Sanda Bawa, Rita Meunier-Prest, Yoann Rousselin, Jean-Pierre Couvercelle, Christine Stern, Bernard Malézieux, and Marcel Bouvet
Royal Society of Chemistry (RSC)
A series of charge transfer complexes (CTCs) were successfully formed by solvent free processing techniques, using the 1,2,4,5-tetracyano benzene (TCNB) as πA molecule and a series of p-dihydroquinones (H2Qs) as πD counterparts.
Yoann Rousselin, Sylvie Yolka, and Alexandre Clavel
International Union of Crystallography (IUCr)
Two polymorphs, (I) and (II), of (S)-{2-[(8S,9S,10R,11S,13S,14S,17R)-11,17-dihydroxy-10,13-dimethyl-3-oxo-2,6,7,8,9,11,12,14,15,16-decahydro-1H-cyclopenta[a]phenanthren-17-yl]-2-oxoethyl} 2,2-dimethylpropanethioate, C26H38O5S, have been identified. They are orthorhombic, non-centrosymmetric (P212121). The structures display layers of molecules conected via O—H...O hydrogen bonds along the b-axis direction in polymorph (I) and along the c-axis direction in polymorph (II). The structure of (II) exhibits disorder of the main molecule.
Michael Knorr, Lydie Viau, Yoann Rousselin, and Marek M. Kubicki
International Union of Crystallography (IUCr)
The polymeric title compound, [Cu2Br2(C4H8S)2] n , CP1, represents an example of a two-dimensional coordination polymer resulting from reaction of CuBr with tetrahydrothiophene (THT) in MeCN solution. The two-dimensional layers consist of two different types of rhomboid-shaped dinuclear Cu(μ2-Br)2Cu secondary building units (SBUs); one with a quite loose Cu...Cu separation of 3.3348 (10) Å and a second one with a much closer intermetallic contact of 2.9044 (9) Å. These SBUs are interconnected through bridging THT ligands, in which the S atom acts as a four-electron donor bridging each Cu(μ2-Br)2Cu unit in a μ2-bonding mode. In the crystal, the layers are linked by very weak C—H...·Br hydrogen bonds with H...Br distances of 2.95 Å, thus giving rise to a three-dimensional supramolecular network.
Benjamin Rousselle, Florence Bouyer, Jérôme Bayardon, Myriam Laly, François Ghiringhelli, Yoann Rousselin, Ewen Bodio, and Raluca Malacea-Kabbara
Royal Society of Chemistry (RSC)
The strong anti-proliferative properties of an original family of gold(i) complexes were assessed (submicromolar range activity).
Jérôme Bayardon, Yoann Rousselin, and Raluca Malacea‐Kabbara
Wiley
AbstractThe stereoselective synthesis of P‐chirogenic diphosphinotriazoles using ephedrine methodology was described. The coordination behavior of these compounds as P,P‐ligands has been demonstrated by the preparation as well as the spectroscopic and X‐ray crystallographic analyses of a palladium complex. The efficiency of these new P‐chirogenic diphosphines in the palladium‐catalyzed asymmetric allylic substitution reaction was also evaluated.
Raoudha Soury, Marwa Chaabene, Mahjoub Jabli, and Yoann Rousselin
Elsevier BV
Adrien Schlachter, Frank Juvenal, Rodolphe Kinghat Tangou, Abderrahim Khatyr, Fabrice Guyon, Paul-Ludovic Karsenti, Carsten Strohmann, Marek M. Kubicki, Yoann Rousselin, Pierre D. Harvey,et al.
Royal Society of Chemistry (RSC)
The S,N-coordination of azabutadienes onto fac-Re(CO)3X species creates moderately emissive complexes, which exhibit ultrafast and multiphasic deactivation kinetics of both their singlet and triplet (MLCT/ILCT) excited states.
Vivian Lioret, Yoann Rousselin, and Richard A. Decréau
Elsevier BV
Antonin Jaillet, Christophe Darcel, Jérôme Bayardon, Adrien Schlachter, Christine Salomon, Yoann Rousselin, Pierre Harvey, and Sylvain Jugé
American Chemical Society (ACS)
We have recently patented an unprecedented stereospecific N→O phosphinyl migration process which transforms P-chirogenic aminophosphines into phosphinites. A fine design of aminophosphine phosphinite ligands (AMPP*) derived from ephedrine and bearing a P-chirogenic center either at the aminophosphine or phosphinite moiety, was performed. The synthesis of AMPP* ligands with P-chirogenic aminophosphine moiety was based on the well-established stereospecific reaction of oxazaphospholidine-borane with organolithium reagents, followed by trapping with a chlorophosphine and borane decomplexation. Concurrently, the preparation of AMPP* ligands with P-chirogenic phosphinite moiety were performed by N→O phosphinyl migration of aminophosphines borane by heating at 50 °C with DABCO, and then reaction with chlorophosphines. AMPP* ligands were studied in palladium-catalyzed asymmetric allylic alkylations, leading to enantioselectivities from 91% (R) to 95% e.e. (S). X-ray crystallographic data for relevant Pd-AMPP* complexes and computer modeling explained the origin of the enantioselectivities based on MO interactions of most stable conformers with nucleophiles.
Jérôme Bayardon, Benjamin Rousselle, Yoann Rousselin, Quentin Bonnin, and Raluca Malacea‐Kabbara
Wiley
Herein we report the synthesis of a new P‐chirogenic triazole‐based phosphine according to the ephedrine methodology. Upon reaction with late transition‐metal derivatives, RhI and PdII, phosphine‐triazole forms complexes with bidentate P,N coordination, as demonstrated by spectroscopic and X‐ray crystallographic analyses. First experiments in asymmetric catalysis showed the catalytic potential of this new chiral P,N‐type ligand.