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Uranyl Photo-Catalyzed Methane C-H Functionalization – UraMeth
UraMeth concerns the use of actinides and particularly uranyl complexes as a promising pioneering family of photo-redox catalysts for HAT processes that are not based on precious platinum group metals. Although much less discussed in the literature, these complexes display high oxidative photo-redox
Bare transition metal nitride nanomaterials synthesized by laser ablation as electrocatalysts of oxygen reactions – NITRECAT
Oxygen (O2) is a key molecule in hydrogen technology devices for energy production. The investigation of its interaction with the electrode surface can help one to better understand several reactions at the electrode-electrolyte interface. In electrocatalysis, oxygen is obtained by water splitting a
Hexafluoroisopropanol: New Reactions and Mechanistic Insight by a Combined Experimental and Theoretical Approach – ElectroHIP
Hexafluoroisopropanol (HFIP) has emerged as a solvent uniquely capable of enabling various challenging yet desirable reactions in organic synthesis. HFIP possesses remarkable intrinsic properties: it can stabilize cationic and radical species and strongly donate hydrogen bonds through the formation
N2 Functionalization using a family of (XCX)M complexes – FuN2
The Haber-Bosch process still stands as one of the most important chemical transformations to mankind. It allows the synthesis of ca 170 million tons/year of ammonia, mostly used as fertilizer, from dinitrogen and dihydrogen using heterogeneous catalyst submitted to drastic conditions, involving hig
Green photocatalytic production of fuel-like hydrocarbons using Fatty Acid Photodecarboxylase – GreenCatFAP
Fatty acid photodecarboxylase (FAP) is one of the few natural photoenzymes described to date. Upon illumination, FAP catalyzes the decarboxylation of long-chain fatty acids (C16-C18), thereby generating hydrocarbons in a single step. Our discovery and initial structural and mechanistic description o
Radiolabeled Bicyclic Peptides with metal chelators as central structural scaffolds – Radio-BIPeps
The project aims to develop new radiopharmaceutical tools for theranostic in nuclear medicine, i.e. for therapeutic and diagnostic applications with a same molecular object. To ensure the specific delivery of the radionuclide to the tumor, the radiometal, that is confined in a chelator, must be coup
A radically new perspective for carbon-carbon bond formation – CO2SAM
CO2 utilization is part of the broad strategy to produce fuels and value-added chemicals in a carbon neutral manner. However, the activation and recycling of CO2 as well as the use of CO2-derived functional groups (CO, –CH3, HCOO- etc.), are very challenging notably when performed in late-stage synt
Reactivities of Electron-Deficient Arenes – EDAReact
This project will use quantitative information about the electrophilic and nucleophilic reactivity of organic molecules to develop unprecedented approaches to organic syntheses through dearomative reactions of electron-deficient arenes (EDAs). To unravel the individual steps of EDA/nucleophile react
Chiral Dienolates for Organocatalytic control over multiple stereogenicities in Atroposelective Synthesis – DINATROP
Organocatalysis now belongs to the classic devices for the chemist’s “green toolbox”. In the context of enantioselective synthesis, if the control of central chirality is a well-established field, the same is not true for axial chirality. Therefore, the development of efficient methodologies to addr
New opportunities in enantioselective borrowing hydrogen – Chiron
Hydrogenation and the related borrowing hydrogen are arguably among the most useful routes for the eco-compatible creation of chiral molecules. While molecular hydrogen can be transferred to preformed unsaturated species through classical hydrogenation and Transfer Hydrogenation (TH), Borrowing Hydr
Asymmetric synthesis of sulfinamidines – SulFourN2
The synthesis of bioactive compounds bearing unconventional functional groups and pharmacophores is a strategic task for pharmaceutical companies. In this context, the access to aza-analogues of sulfur derivatives is a great opportunity to obtain improved drug properties in terms of solubility, acti
Sydnones Derivatives as Bioorthogonal Caged Electrophiles for Permanent Fluorescent Labelling – SydFluo
Mesoionic compounds represent an old family of dipoles whose reactivity has been under-exploited since their discovery almost a century ago. Among these compounds, sydnones are undoubtedly the best known and most widely used mesoionics, especially for the synthesis of pyrazoles by thermal cycloaddit
Intracellular Delivery by Out-of-Equilibrium FoldAmers – IDEA
The effective and safe intracellular delivery of new pharmaceutical ingredients represent a major hurdle in the translation of biomedical discoveries to applications in the clinic. Cell-penetrating peptides are promising vectors but critical issues such as lack of selectivity and systemic toxicity h
Toward novel REActivity in Carbene Transfer reactions provided by PHTHALocyanine catalysts – REACTPHTHAL
CCarbene transfer to X-H bonds (X=N, C, S, Si) has emerged as a powerful strategy for construction of elaborated molecules. These versatile and atom-economic reactions are efficiently catalyzed by porphyrin complexes and engineered hemoproteins and involve carbenoid metal species. In contrast, cheap
Multi-functional catalysts for solar light-assisted water treatment – MULTICAT
Water treatment is an urgent worldwide health issue that scientists must address. Catalytic Advanced Oxidation Processes (AOP) are promising technologies to meet the challenges of water remediation, as conventional treatments in place fail in removing efficiently a wide span of high-concern hazardou
Orthogonal dynamic assembly for peptidic engineering – OrthoPep
Cyclopeptides are an interesting class of therapeutics to target protein-protein interactions (PPIs) considering their non-toxicity, stability, and ability to mimic the large interacting domain of a protein. But, their rational molecular design is not straightforward, and their sequence optimization
C-C bond forming enzymes to convert imines into amines: towards “aldaminases” – ALDAMINASE
Discovering cutting-edge methods for the synthesis of chiral amines is essential since many pharmaceutical molecules contain this motif. Moreover, to meet the challenges of sustainability, it is imperative to develop green, chemo-, regio- and stereo-selective processes. Biocatalysis meets its expect
Atroposelective synthesis of heterobiaryls using supramolecular photoredox organocatalysts – AtropoPhotoCat
Atropoisomers are an important class of chiral molecules whose enantioselective synthesis often represents a challenge and require the development of efficient original, highly selective, and environmentally-friendly reactions. The present project is in this vein, by proposing a supramolecular appro
Leveraging Chemoselectivity with Carbene-Derived Earth-Abundant Polynuclear Metal-Hydride – CarbHydride
As exemplified by the Stryker’s reagent, a phosphine-stabilized hexameric polymetallic copper(I) hydride [(Ph3P)CuH]6 (commercialized by Aldrich) routinely used in stoichiometric or catalytic quantities as a mild and selective reducing agent, Metal-Hydrogen (M-H) bonds occupy an important place in o
Cationic OrganoAcids: pushing the Limits for Applications in Synthesis – COALAS
Many important transformations in organic chemistry involve transient cationic intermediates where the nature of the associated anion is of utmost importance to control the reactivity and selectivities. In this project, we plan to focus on the development of cationic Brønsted organoacids that featur
Super-reduced polyoxometalates: structural elucidation, solution behavior and coordination properties – POMEROL
Polyoxometalates (POMs) correspond to a class of compounds built from early transition-metals (V, Mo and W). Although not really understand, one of the most striking properties of POMs is their ability to exchange massively electrons, making them appealing components to design electrochemical energy
Exploring radical gold bis(dithiolene) complexes as NIR-II absorbers – NIR-ABS
Within this NIR-ABS project, we aim at developing an extended library of coordination complexes with a strong absorption in the NIR-II region as an emerging class of attractive molecules with interesting photothermal properties. Near Infra-Red (NIR) light spanning from 780 to 2500 nm carries importa
Phosphine allene Ligands: Coordination and Catalytic Applications – PALCOCA
Access to new phosphines as chiral ligands by modulating their electronic and geometrical properties is a major challenge in the field of asymmetric catalysis to obtain optically pure compounds of interest. Diphosphines with axial chirality meet these requirements. However, the axial chirality of al
Coordination chemistry in supercritical fluids: from post-synthetic modifications to the synthesis of functional networks – CoordinSCFs
This project proposes to combine the versatilities of coordination chemistry and supercritical fluids (SCFs) for the development of innovative strategies toward the synthesis of molecule-based functional coordination polymers (CPs). Focusing on metal/pyrazine-based systems, the first objectives usin
Deep Eutectic Solvents as media for the preparation of catalytically active Covalent Organic Frameworks – DEEPCatCOF
Associating three research groups with complementary expertise, the DEEPCatCOF project addresses two underexplored green aspects of porous materials of covalent-organic frameworks (COFs) type: i) the use of an emerging class of green media, deep eutectic solvents (DES) – cousins of ionic liquids – f
Ultrafused dipyromethene borate complexes for deep NIR applications – ULBONIR
The project aim is to develop optimised fused dipyromethen-borate (BODIPY) presenting high fluorescence in the NIR-I and NIR-II regions. These areas of the electromagnetic radiation present highly desirable feature for applications in biolabeling, microscopy and image-guided surgery such as minimize
Access to inter-nucleoside C-C links by metal-catalyzed cross-coupling reactions on glycal-type nucleosides – CatACLiSM
The importance of oligonucleotides (ON) pushed chemists to develop powerful syntheses to build them. Currently, the access to natural ON has become an efficient automated process. Nevertheless, the natural link is rapidly hydrolyzed in physiological media. Unnatural ON were thus explored to reach mo
Bio-inspired soft organocatalysis inaqueous coacervate droplets – CHEMinDROPS
Advances in modern synthetic chemistry must comply with the need for a lower environmental impact, which has led in recent years to the development of a softer chemistry drawing inspiration from Nature. The formation of C-C bonds, which often requires the use of metals and organic solvents, is a cen
Nickel ate-complexes as ion pairs in catalysis – Nickelate
“Nickelate” project intends to explore the full potential of novel Nickel derived ate-complexes in the field of modern catalysis. The design of these catalysts and the optimization of their abilities in diastereo- and enantioselective transformations are envisioned through various C-H functionalizat
Synthesis of new cryptophanes: toward xenon-MRI biosensor and beyond – Neo-Crypto
Cryptophanes (Crs) are cage-like host molecules composed of two molecular crowns, cyclotriveratrylene (CTV) units usually connected by three ether linkers. These molecular hosts are known since decades to be able to encapsulate many different entities, in particular they are well suited for xenon. T
2-Pyridylidenes Ligands for Iron Catalysis – 2Pyr4FeCat
Since their discovery, N-Heterocyclic Carbene (NHC) ligands were subjected to an impressive development in organometallic catalysis, leading to a successful use in many metal-catalysed transformations. Despite remarkable breakthroughs achieved to date, the design of complementary architectures, disp
Fluorinated phosphoramidite synthesis for the development of new oligonucleotides with improved stability and hydrophobicity – FluoPHOS
Nucleic acid-based therapeutics have emerged and represent today, key targets in a wide range of diseases. Since natural oligonucleotides (ONs) are rapidly metabolized in biological media by nucleases and suffer from a poor cellular uptake, several chemical modifications were envisaged and led to th
CYCLoadditions involving 2-pyrONEs: a powerful tool to access molecular complexity – CYCLONE
Ce projet vise au développement de la chimie des cycloadditions de 2-pyrones et à leur application pour la synthèse énantiosélective de structures moléculaires complexes. Pour cela, trois axes principaux seront développés. Dans une première partie, les lactones bicycliques issues des réactions énant
Gold(III) chemistry beyond ground-state – GOLD3STAR
Spectacular progress has been achieved recently in the organometallic chemistry of gold. Ligands have been shown to be of paramount importance to stabilize highly reactive gold complexes and unlock elementary transformations considered so far highly disfavoured, if not impossible at gold. However, v
Redox Chemistry towards an Access to Polyfluorinated Alkylamines – RedAF
Organofluorine chemistry became a research of paramount importance as fluorinated molecules are prevalent derivatives in pharmaceutical, agrochemical industries and material sciences. Of particular relevance is the emergence of trifluoromethylated alkylamines. Indeed, the trifluoromethyl moiety near
Macrocyclic ligands gIving access to robust photosensitizers based on copper complexes – MagicCopper
The MagicCopper project focuses on the preparation and study of robust copper(I) complexes with enhanced photophysical properties and displaying redox reversibility between the copper(I) and copper(II) states. Macrocyclic diphosphine and terpyridine ligands will be used to ensure the stabilization o
Flow multiphasic catalysis with polymeric nanoreactors – FlowNanoCat
The increase of societal concern about our planet future led to the 12 principles of Green Chemistry. In this global scheme, catalysis plays a central role for a more sustainable chemical industry. Although heterogeneous catalysis is largely implemented in industry, homogeneous catalysis remains hig
Polyoxometalate-based hybrid molecular materials for antibacterial photodynamic therapy in the visible region – PolyBact
The growing resistance of bacteria to antibiotics, responsible for approximately 5 million deaths in 2019, requires the development of new antibacterial agents and/or new therapeutic strategies. Photodynamic therapy (PDT), consisting in the generation via a photosensitizer (PS) of reactive oxygen sp
-Hyper-positive nonlinear effects in asymmetric catalysis: elucidating principals and applications. – Hyp-NLE
Nonlinear effects in asymmetric catalysis are a fascinating and important phenomenon, especially for rationalizing the occurrence of homochirality in life. Nonlinear effects are also an important tool for understanding the mechanism of an asymmetric reaction. In this framework, we have recently disc
Towards the ultimate lanthanide metallocene single molecule magnets – UltimSMM
UltimSMM project proposes original synthetic pathways to generate ideal lanthanide-based sandwich metallocene complexes towards ground-breaking insights into the field of lanthanide Single Molecule Magnets (SMMs). Bulky cyclopentadienyl-based trivalent dysprosium complexes have recently led to impre
Enantioselective Tethered Counterion-Directed Catalysis – TCDCat
The necessity to access chiral molecules by targeting a given enantiomer is of utmost importance. As a result, transition metal catalysis with complexes bearing chiral ligands has become the best ally of synthetic chemists. This ligand-based approach often relies on the use of highly bulky ligands t
Selective C-H bonds activation reactions catalyzed by N-heterocyclic carbene metal complexes linked to porphyrins – SCARY-NHC
C-H bond activation reactions can have important applications and economic benefits. The most complicated challenge to take up in this field is the selective activation of C-H bonds relative to others within a substrate. Pyridine derivatives are privileged scaffold in medicinal chemistry and selecti
Supramolecular Capsules and Cages for Circularly Polarized Luminescence – SupraCPL
During the last decades, extensive work focused on the design of molecular systems displaying circularly polarised luminescence (CPL). A chiral light emitter shows different right- and left-handed circularly polarised emission which gives birth to CPL. CPL is key for the enhancement of CP-OLED scree
Reactivity of metal complexes in confined spaces – CONFICAT
The CONFICAT project aims at exploring the reactivity of transition metal (particularly gold) complexes in confined environments. The main concept is to generate, stabilize and use cationic metal complexes within anionic supramolecular cages. Although this strategy has started to be explored recentl
Aziridines stereocontroled ring-opening for high molecular complexity and diversity – ASTERO
The project aims i) at studying the potential of aziridines as starting point for the enantioselective synthesis of more complex, polyfunctionalized molecules with a tetrasubstituted stereogenic center and ii) at understanding the different mechanisms governing the regioselectivity of these transfor
Turbocharged Chemical Protein Synthesis – Turbo
In recent years, chemical protein synthesis enabled the production of homogeneous batches of large and highly decorated protein targets. In doing so, it has provided the means for successful applications in chemical biology, medicinal chemistry, materials science and nanotechnology research. Chemic
Exploring the Origin of Molecular Homochirality through Magneto-Chiral Photochemistry – PRINCIPE
Life homochirality consists in the exclusive production and use of homochiral molecular building blocks (L-amino acids and D-sugars) for the fabrication of biological polymers. Why homochirality has prevailed over a combination of left- and right-handed molecules and which symmetry breaking process
Lanthanide Complexes for the Transformation of CO into Value-Added Multicarbon Products – MultiCO
Nature has the ability to selectively and efficiently transform simple, inert building blocks into highly functionalised molecules. The amino acid family is a representative example, featuring a multicarbon (C2+) backbone and various functional groups. Although the activation of small molecules such
Cooperative N-heterocyclic carbene/transition metal redox catalysis – COORECA
Aldehydes are key synthons in organic synthesis. They are known to react with N-heterocyclic carbenes (NHC) to form electron-rich Breslow intermediates which are capable of triggering single-electron transfer reactions. Related NHC-catalysed radical transformations of aldehydes constitute an emergin
Lanthano-peptides as mimics of lanthanide methanol dehydrogenase enZYME – LnZYME
LnZYME aims to design well-folded lanthano-peptides able to reproduce the structure of the active-site of the sole enzyme known standing on lanthanide, the Lanthanide-Methanol DeHydrogenase (Ln-MDH). The few organic molecular mimics described so far failed to reproduce Ln-MDH activity. Better mimics
Fluorinated Cyclopropane Amino Acids: from Synthesis to structural Implication in peptides for biological Applications – FLUORAAC
The FLUORAAC project aims to develop original accesses to cyclopropane amino acids bearing fluorinated groups (CF3, CF2H and CH2F) or a fluorine atom from nitro diazo acetates and alkenes bearing a fluorinated group. Other methodologies from diazo compounds bearing a CF3 or CF2H group and from an al
Switching Magneto-Chiral Dichroism in Lanthanide Single Molecule Magnets – SWITCH-MChD
Lanthanide complexes are at the heart of these researches because they combine large magnetic moment and strong magnetic anisotropy due to the large orbital contribution to the magnetic moment and spin-orbit coupling and unique optical properties. It has indeed been proven very recently that the mag