A5060271055- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Catalytic Cross-Coupling Reactions
- Synthetic Organic Chemistry Methods
- Supramolecular Chemistry and Complexes
- Axial and Atropisomeric Chirality Synthesis
- Chemical Synthesis and Analysis
- Asymmetric Hydrogenation and Catalysis
- Luminescence and Fluorescent Materials
- Molecular Sensors and Ion Detection
- Molecular spectroscopy and chirality
- Supramolecular Self-Assembly in Materials
- Synthesis and Properties of Aromatic Compounds
- Organoboron and organosilicon chemistry
- Click Chemistry and Applications
- Carbohydrate Chemistry and Synthesis
- Crystallography and molecular interactions
- Analytical Chemistry and Chromatography
- Asymmetric Synthesis and Catalysis
- DNA and Nucleic Acid Chemistry
- Advanced NMR Techniques and Applications
- Cyclopropane Reaction Mechanisms
- Synthesis and Catalytic Reactions
- Electron Spin Resonance Studies
Aix-Marseille Université
2019-2025
Centrale Marseille
2017-2023
Centre National de la Recherche Scientifique
2017-2023
Institut des Sciences Moléculaires de Marseille
2018-2023
Clariant (Switzerland)
2003-2011
A steric scale of 20 recurrent groups was established from comparison rotational barriers on N-(o-substituted aryl)thiazoline-2-thione atropisomers. The resulting energy activation ΔG⧧rot reflects the spatial requirement ortho substituent borne by aryl moiety, electronic aspects and external parameters (temperature solvent) generating negligible contributions. Concerning divergent rankings reported in literature, great sensitivity this model allowed us to show unambiguously that a methyl...
Well-defined optically pure transition metal (TM) complexes bearing C1- and C2-symmetric N-heterocyclic carbene (NHC) ligands were prepared from prochiral NHC precursors. As predicted by DFT calculations, our strategy capitalizes on the formation of a metal-carbene bond which induces an axis chirality. Configurationally stable atropisomers various NHC-containing TM isolated preparative HPLC chiral stationary phase in good yields excellent optical purities (up to 99.5% ee). The transfer Cu...
The synthesis, properties and structural requirements for atropisomerism at the C−B bond in boron Lewis acids such as triarylboranes have been understudied so far. We report first series of atropisomeric constituted a naphthyl rotor dihydro‐9‐bora‐anthracenyl stator subunits, connected by stereogenic axis. Through systematic crystallographic, kinetic, photophysical quantum chemical studies, mechanisms, rates barriers diastereomerization enantiomerization were determined. orthogonal...
The synthesis, properties and structural requirements for atropisomerism at the C−B bond in boron Lewis acids such as triarylboranes have been understudied so far. We report first series of atropisomeric constituted a naphthyl rotor dihydro‐9‐bora‐anthracenyl stator subunits, connected by stereogenic axis. Through systematic crystallographic, kinetic, photophysical quantum chemical studies, mechanisms, rates barriers diastereomerization enantiomerization were determined. orthogonal...
A new chiral hemicryptophane cage combining an electron-rich cyclotriveratrylene (CTV) unit and polar amine functions has been synthesized. The resolution of the racemic mixture performed by HPLC, assignment absolute configuration two enantiomers achieved using ECD spectroscopy. In contrast with other receptors, enantiomeric hosts display both remarkable enantioselectivities in recognition carbohydrates good binding constants. Moreover, switching chirality CTV from M to P, a strong...
A set of 16 chiral ruthenium complexes containing atropisomerically stable N-Heterocyclic Carbene (NHC) ligands was synthesized from prochiral NHC precursors. After a rapid screening in asymmetric ring-opening-cross metathesis (AROCM), the most effective atrop BIAN-NHC Ru-catalyst (up to 97 : 3 er) then converted Z-selective catechodithiolate complex. The latter proved be highly efficient AROCM exo-norbornenes affording valuable trans-cyclopentanes with excellent Z-selectivity (>98 %) and...
This paper aims at designing chromophores with efficient aggregation-induced emission (AIE) properties for two-photon fluorescence microscopy (2PFM), which is one of the best-suited types imaging living organisms or thick biological tissues. Tetraphenylethylene (TPE) derivatives are common building blocks in design AIE properties. Therefore, this study, extended TPE AIEgens specifically optimized absorption (2PA) synthesized and resulting (E/Z) isomers separated using chromatography on...
Enzymatic trigger. Upon enzymatic hydrolysis by Subtilisin A, highly stable alkoxyamines are transformed into labile able to homolyze spontaneously in less than 500 seconds, at 37 °C.
Cyclotriveratrylene (CTV) is a macrocyclic cyclophane presenting bowl-shaped conformation, used as building block to construct cryptophane and hemicryptophane capsules. A method synthesize new enantiopure CTV derivatives with an unprecedented spatial arrangement of their substituents, exhibiting C1 symmetry, described. The absolute configuration was assigned by ECD spectroscopy coupled modeling. statistical model has allowed for optimization the proportion CTV, modularity this approach also...
Abstract The five‐steps synthesis of a hemicryptophane cage combining benzene‐1,3,5‐tricarboxamide unit and cyclotriveratrylene (CTV) moiety is described. Chiral high‐performance liquid chromatography (HPLC) was used to resolve the racemic mixture. absolute configuration isolated enantiomers assigned by comparison experimental electronic circular dichroism (ECD) spectra with calculated ones. X‐ray molecular structures reveal that capped adopts structurally chiral conformation in solid state:...
From achiral imidazolinium salts, chiral transition metal complexes containing an N-heterocyclic carbene (NHC) ligand were prepared (metal = palladium, copper, silver, gold, rhodium). Axial chirality in these results from the formation of metal-carbene bond leading to restriction rotation dissymmetric N-aryl substituents about C-N bond. When exhibited a sufficient configurational stability, resolution by high-performance liquid chromatography (HPLC) on preparative scale enabled isolation...
The synthesis of P-stereogenic aminophosphine-boranes has been developed on the basis umpolung reactivity in situ generated alkylarylphosphido-boranes, which are normally configurationally unstable intermediates. In our case, their high configurational stability was due to slow release hydroxyalkyl protecting group, together with fast formation iodophosphanylborane presence N-iodosuccinimide. subsequent substitution reaction found proceed moderate good yields and a very stereospecifity (es)...
Abstract Herein, we report a general method for quantitative measurement of the configurational stability stereogenic nitrogen coordinated to M (II) in corresponding square planar complexes. This stereochemical approach is quite sensitive steric and electronic effects substituents shown work well Ni(II), Pd(II), Cu(II) Structural simplicity compounds used, coupled with high sensitivity reliability experimental procedures, bodes application this evaluation chemical properties newly designed...
Abstract Series of chiral palladium(II) allyl and cinnamyl complexes bearing a C 1 ‐symmetric N‐heterocyclic carbenes were synthesized from achiral precursors. The chirality theses results the formation carbene‐palladium bond which restricts rotation dissymmetric N ‐aryl substituents NHC thus creates an axis chirality. Chiral HPLC at preparative scale enabled resolution racemic provided straightforward access to with excellent enantiopurities (>99.5% ee). Enantiopure studied by crystal...
The (Z) and (E)-isomers of an extended tetraphenylethylene-based chromophore with optimized two-photon-induced luminescence properties are separated functionalized water-solubilizing pendant polymer groups, promoting their self-assembly in physiological media the form small, colloidal stable organic nanoparticles. two resulting fluorescent suspensions then evaluated as potential two-photon luminescent contrast agents for intravital epifluorescence fluorescence microscopy. Comparisons...
Abstract The design of molecular cages with low symmetry could allow for more specific tuning their properties and better mimic the unsymmetrical complex environment protein pockets. However, added value lowering receptors has been rarely demonstrated. Herein, C 3 ‐ 1 ‐symmetrical cages, presenting same recognition sites, have synthesized investigated as hosts carbohydrate recognition. Structurally related derivatives glucose, galactose mannose were found to greater affinity receptor lowest...
Two new hemicryptophanes combining a cyclotriveratrylene unit with either an aminotrisamide or tris(2-aminoethyl)amine (tren) moiety have been synthesized. Although conventional synthesis approach was used, the molecular cages obtained are devoid of expected C3 symmetry. NMR analyses and X-ray crystal structure determination showed that these exhibited C1 symmetry due to unusual arrangement substituents unit. This unprecedented is related change in regioselectivity Friedel-Crafts reactions...
Abstract In order to facilitate the synthesis of NHC precursors as well incorporate new moieties, influence backbone substitution was investigated within concept atropisomeric NHC‐metal complexes. A series prepared from anilines and used synthesize corresponding Pd(allyl)Cl(NHC) complexes, most time a mixture diastereomers ( meso chiral). Chiral HPLC at preparative scale enabled obtain enantiopure complexes in low excellent yields. These displayed good activity intramolecular α‐arylation...
The concept of atropisomeric N-heterocyclic carbene (NHC)-metal complexes was extended to NHCs possessing a C2-symmetry and implemented prepare palladium-based complexes. An in-depth study the NHC precursors screening various ligands enabled us circumvent issue associated with formation meso A set 8 NHC-palladium were prepared then obtained high enantiopurities, thanks an efficient resolution by chiral HPLC at preparative scale. These displayed good activity in intramolecular α-arylation...