Clément Denhez

Université de Reims Champagne-Ardenne

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Jean‐Luc Vasse

Centre National de la Recherche Scientifique

Jan Szymoniak

Institut de Chimie Moléculaire de Reims

Dom Guillaume

Institut de Chimie Moléculaire de Reims

Dominique Harakat

Centre National de la Recherche Scientifique

Dominique Guillaume

Institut de Chimie Moléculaire de Reims

Hatice Berber

Université de Reims Champagne-Ardenne

Pédro Lameiras

Université de Reims Champagne-Ardenne

Alexandre Vasseur

Centre National de la Recherche Scientifique

Pascale Clivio

Université de Reims Champagne-Ardenne

Alexandre Pierret

Université de Lorraine

Cooperative Institutions

Centre National de la Recherche Scientifique

Université de Reims Champagne-Ardenne

Institut de Chimie Moléculaire de Reims

Laboratoire des Biomolécules

Laboratoire de Chimie Organique

Université Paris Cité

Université Paris-Sud

Institut de Chimie des Substances Naturelles

Laboratoire de Chimie

Université de Lorraine

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Atropisomerism about aryl–C(sp³) bonds: chemically driven rotational pathway in cannabidiol derivatives

Organic & Biomolecular Chemistry (2023)

Clément Denhez Pédro Lameiras Hatice Berber

Among the two possible pathways to reach ( M ) and ( P ) conformers in CBD derivatives, the rotation through TS1 is preferred in arylcyclohexene and TS2 in arylcyclohexane series.

Atropisomer

Conformational isomerism

10.1039/d3ob01617j

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Selective enhancement of (6–4) photoproduct formation in dithymine dinucleotides driven by specific sugar puckering

Organic & Biomolecular Chemistry (2024)

Jouda Jakhlal Clément Denhez Stéphanie Castex Agathe Martinez Dominique Harakat

Four dinucleotide analogs of thymidylyl(3'-5')thymidine (TpT) have been designed and synthesized with a view to increase the selectivity, with respect to CPD, of efficient UV-induced (6-4) photoproduct formation. The deoxyribose residues of these analogs have been modified to increase north and south conformer populations at 5'- and 3'-ends, respectively. Dinucleotides whose 5'-end north population exceeds

Deoxyribose

Thymidine

Conformational isomerism

10.1039/d4ob00279b

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Can Fruit-form be a Marker for Argan Oil Production?

Natural Product Communications (2013)

Saïd Gharby Hicham Harhar Badr Eddine Kartah Hanae El Monfalouti Clément Denhez

Deforestation is an important matter for the argan forest whose preservation necessitates planting trees. Macroscopic parameters are urgently needed to identify trees presenting good potential as oil producers. This study demonstrates that argan oil produced from kernels of apiculate fruit is richer in d-tocopherol, whereas oil produced from spherical fruit is richer in linoleic acid, and that produced from fusiform fruit is richer in oleic acid. Therefore, the use of fruit-form as a marker could permit an easy organic production of "naturally enriched" oils.

10.1177/1934578x1300800106

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Citations (13)

Multimetallic Zirconocene-Based Catalysis: Alkyne Dimerization and Cyclotrimerization Reactions

Organometallics (2008)

Antoine Joosten Mohamad Soueidan Clément Denhez Dominique Harakat Florence Hélion

Systematic exploration of zirconocene (Cp2ZrII) chemistry since the 1980s has offered a wide range of useful methods for organic synthesis. Many of these reactions are stoichiometric in zirconium, and even if several catalytic reactions are known, the development of catalytic zirconocene chemistry is of continuing interest. In this paper, the study of reactions catalytic in zirconium, i.e. alkyne dimerization and cyclotrimerization, is presented. These reactions are carried out by employing the recently introduced lanthanide-originated zirconocene equivalent. The use of 10 mol % of Cp2ZrCl2, together with La metal or mischmetall as reductant and AlCl3 as transmetalating agent, leads to an efficient formation of dienes from disubstituted alkynes. Under the same conditions, monosubstituted alkynes underwent cyclotrimerization reactions to afford benzene derivatives. This reaction also occurs efficiently in the absence of AlCl3. It was postulated that the catalytic cyclotrimerization did not proceed through a typical insertion of the alkyne into the zirconacyclopentadiene intermediate. This unprecedented reaction takes place in the presence of zirconocene and lanthanide species, possibly involving a bimetallic polarization process.

Alkyne

Bimetallic strip

Stoichiometry

10.1021/om8002703

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Citations (25)

Revisiting the Sweet Taste Receptor T1R2-T1R3 through Molecular Dynamics Simulations Coupled with a Noncovalent Interactions Analysis

The Journal of Physical Chemistry B (2023)

Wilfredo Evangelista Clément Denhez Angélica M. Baena‐Moncada Miguel Ponce‐Vargas

It is nowadays widely accepted that sweet taste perception is elicited by the activation of the heterodimeric complex T1R2-T1R3, customarily known as sweet taste receptor (STR). However, the interplay between STR and sweeteners has not yet been fully clarified. Here through a methodology coupling molecular dynamics and the independent gradient model (igm) approach we determine the main interacting signatures of the closed (active) conformation of the T1R2 Venus flytrap domain (VFD) toward aspartame. The igm methodology provides a rapid and reliable quantification of noncovalent interactions through a score (Δginter) based on the attenuation of the electronic density gradient when two molecular fragments approach each other. Herein, this approach is coupled to a 100 ns molecular dynamics simulation (MD-igm) to explore the ligand-cavity contacts on a per-residue basis as well as a series of key inter-residue interactions that stabilize the closed form of VFD. We also apply an atomic decomposition scheme of noncovalent interactions to quantify the contribution of the ligand segments to the noncovalent interplay. Finally, a series of structural modification on aspartame are conducted in order to obtain guidelines for the rational design of novel sweeteners. Given that innovative methodologies to reliably quantify the extent of ligand-protein coupling are strongly demanded, this approach combining a noncovalent analysis and MD simulations represents a valuable contribution, that can be easily applied to other relevant biomolecular systems.

Non-covalent interactions

Docking (animal)

Aspartame

10.1021/acs.jpcb.2c07180

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Nouvelles méthodes de génération et d'activation de complexes zirconocènes : Synthèse de composés azotés

Clément Denhez

Ce memoire concerne le developpement de nouvelles methodes d’activation de complexes zirconocenes reposant sur une cooperation bimetallique. Cette demarche a ete appliquee a la synthese de composes azotes. La premiere partie de ce travail est consacree au developpement d’une reaction hautement chimioselective de carboalumination d’aldimines sous catalyse au zirconium. Cette reaction met en jeu des alanes en tant que source de groupements alkyls et procede via l’etablissement d’un complexe bimetallique. Dans le cas des imines derivees de l’aniline une reaction d’acylation regioselective en position ortho, egalement catalysee par le zirconium, peut etre mise en oeuvre. Dans la deuxieme partie, nous avons developpe une synthese diastereoselective de pyrrolidines substituees en position 2- et 2,5-. Celles-ci sont obtenues a partir de Nallyloxazolidines optiquement pures selon une sequence d’hydrozirconation / cyclisation activee par un acide de Lewis. Au cours du troisieme chapitre, nous avons developpe une methode de preparation stereoselective de γ-lactames via une reaction de couplage intramoleculaire de carbamates homoallyliques impliquant la chimie du zirconium(II). Enfin, la derniere partie de cette these a ete consacree au developpement d’un nouveau reactif, equivalent synthetique du zirconocene(II). Celui-ci est obtenu par reduction du dichlorure de zirconocene par un alliage de lanthanides, le mischmetall. Ce nouveau reactif a montre un fort potentiel synthetique dans de nombreux couplages et a notamment permis d’utiliser, pour la premiere fois, des alcynes vrais et de realiser la premiere trimerisation d’alcynes catalysee par le zirconium.

Source

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CCDC 1939031: Experimental Crystal Structure Determination

The Cambridge Structural Database (2019)

Clément Denhez Pédro Lameiras Hatice Berber

10.5517/ccdc.csd.cc232qdb

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Intramolecular OH/π versus C–H/O H-Bond-Dependent Conformational Control about Aryl–C(sp³) Bonds in Cannabidiol Derivatives

Organic Letters (2019)

Clément Denhez Pédro Lameiras Hatice Berber

Conformational control in cannabidiol derivatives has been studied by NMR, XRD, and DFT. The stabilization of their axial M and P conformations about the aryl-C(sp3) bond is an effect of competing intramolecular OH/π and CH/O H-bonds. In a nonpolar solvent and in the solid state, the OH/π bond is a determinant of the M conformation. In polar solvents, the CH/O H-bond shifts the equilibrium toward the P conformer because of the breaking of the OH/π bond.

10.1021/acs.orglett.9b02484

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Citations (10)

Structure-Based Kinetic Control in a Domino Process: A Powerful Tool Toward Molecular Diversity in Chromone Series

The Journal of Organic Chemistry (2017)

Thomas Lepitre Clément Denhez Ján Moncóľ Mohamed Othman Ata Martin Lawson

Two successive original routes leading to two novel families of polyheterocycles starting from the versatile chromone-based Michael acceptors platform are reported herein. The major aspect of this work is the selective access to these frameworks by changing the course of the domino process involved in their formation. First, enaminochromanones were selectively accessed under uncommon kinetic control. In this study, we showed that the tuning of the selectivity toward the kinetic product could be achieved by key structural modifications of the different reaction partners involved in the domino process. Once selectivity was efficiently controlled, enaminochromanones were ultimately transformed into a more complex family of polyheterocycles containing the pyrrolo-oxazinone framework. Here, the modulation of the domino sequence toward these particularly scarce structures was enabled by a pivotal switch in reactivity induced by aryl-λ3-iodanes.

Domino

Chromone

10.1021/acs.joc.7b01996

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Citations (9)

Atropisomerism about Aryl–Csp³ Bonds: The Electronic and Steric Influence of ortho-Substituents on Conformational Exchange in Cannabidiol and Linderatin Derivatives

The Journal of Organic Chemistry (2014)

Hatice Berber Pédro Lameiras Clément Denhez Cyril Antheaume Jonathan Clayden

Terpenylation reactions of substituted phenols were used to prepare cannabidiol and linderatin derivatives, and their structure and conformational behavior in solution were investigated by NMR and, for some representative examples, by DFT. VT-NMR spectra and DFT calculations were used to determine the activation energies of the conformational change arising from restricted rotation about the aryl–Csp3 bond that lead to two unequally populated rotameric epimers. The NBO calculation was applied to explain the electronic stabilization of one conformer over another by donor–acceptor charge transfer interactions. Conformational control arises from a combination of stereoelectronic and steric effects between substituents in close contact with each other on the two rings of the endocyclic epoxide atropisomers. This study represents the first exploration of the stereoelectronic origins of atropisomerism around C(sp2)–C(sp3) single bonds through theoretical calculations.

Atropisomer

Electronic effect

10.1021/jo5006069

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Citations (18)